WO2020196273A1 - Polyphenylene sulfide resin composition and molded article - Google Patents

Polyphenylene sulfide resin composition and molded article Download PDF

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Publication number
WO2020196273A1
WO2020196273A1 PCT/JP2020/012317 JP2020012317W WO2020196273A1 WO 2020196273 A1 WO2020196273 A1 WO 2020196273A1 JP 2020012317 W JP2020012317 W JP 2020012317W WO 2020196273 A1 WO2020196273 A1 WO 2020196273A1
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weight
polyphenylene sulfide
parts
sulfide resin
resin composition
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PCT/JP2020/012317
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French (fr)
Japanese (ja)
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徳住啓太
大久保和哉
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東レ株式会社
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Priority to EP20779580.8A priority Critical patent/EP3950811A4/en
Priority to US17/440,262 priority patent/US20220010073A1/en
Priority to CN202080018576.4A priority patent/CN113557266B/en
Priority to KR1020217029345A priority patent/KR20210148112A/en
Priority to JP2020517402A priority patent/JPWO2020196273A1/ja
Publication of WO2020196273A1 publication Critical patent/WO2020196273A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/025—Preparatory processes
    • C08G75/0259—Preparatory processes metal hydrogensulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive

Definitions

  • the present invention relates to a polyphenylene sulfide resin composition which is excellent in mechanical properties and dimensional stability, particularly in which anisotropy is significantly suppressed and expansion during wet heat treatment is suppressed.
  • Polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin is an engineering plastic with excellent heat resistance, flame retardancy, chemical resistance, electrical insulation, moisture heat resistance, mechanical strength and dimensional stability, and is injection molded. Since it can be molded into various molded products, fibers, and films by various molding methods such as extrusion molding and extrusion molding, it is practically used in a wide range of fields such as electric / electronic parts, mechanical parts, and automobile parts.
  • the PPS resin composition in which the PPS resin is reinforced with the fibrous inorganic filler is subjected to thermal expansion, mechanical strength, and continuous stress due to the orientation of the fibrous inorganic filler. Since anisotropy appears with respect to the amount of plastic deformation, the degree of freedom in design is lower than that of metal, and there are cases where restrictions are applied. Further, although the PPS resin has low water absorption, it has a drawback that it cannot maintain its original dimensions because it expands in a moist heat environment.
  • precision parts such as electronic parts and camera parts have a small amount of gas generated during molding (low gas contamination) in addition to mechanical strength and flame retardancy, and a small amount of plastic deformation with respect to applied stress, which is anisotropic. It is desired that there is no property (low anisotropy), and that the swelling in a moist heat environment is small (low moist heat expansion).
  • Patent Document 1 clearly states that the anisotropy of molding shrinkage is improved, since polycarbonate is used, the expansion in a moist heat environment is large, and precise dimensional control of the molded product cannot be performed.
  • Patent Documents 2 and 3 also clearly indicate the improvement in dimensional stability, but since only flat glass fibers are used, there is an expansion difference between the resin flow direction during molding and the direction perpendicular to the flow when the temperature changes. It will come out.
  • the PPS resin is excellent in dimensional stability and low anisotropy without significantly impairing various physical properties such as mechanical properties and chemical resistance, and swelling during wet heat treatment is suppressed.
  • An object of the present invention is to obtain a PPS resin composition.
  • the polyphenylene sulfide resin composition of the present invention has any of the following configurations [1] and [2]. That is, [1] For 100 parts by weight of (A) polyphenylene sulfide resin, 100 to 250 parts by weight of (B) irregularly shaped cross-sectional glass fiber, and (C) non-satisfying (Ca) and (Cb) below.
  • Polyphenylene sulfide resin composition wherein the ratio X / Y of is greater than 1 and less than 7.
  • Mohs hardness is more than 2 and less than 4
  • Melting point or softening point is 380 ° C or more, or [2]
  • A polyphenylene sulfide resin
  • B irregularly shaped cross-section glass fiber
  • C non-fiber inorganic filler
  • Talk, magnesium oxide, and aluminum nitride are blended in 25 to 150 parts by weight in a polyphenylene sulfide resin composition, wherein the blended weight X of the (B) modified cross-sectional glass fiber and the (C) non-fiber A polyphenylene sulfide resin composition, wherein the ratio X / Y to the compounding weight Y of the system-inorganic filler is greater than 1 and less than 7.
  • the molded product of the present invention has the following constitution. That is, A molded product made of the above-mentioned polyphenylene sulfide resin composition.
  • the ratio of the major axis (the longest linear distance in the cross section) to the minor axis (the longest linear distance in the direction perpendicular to the major axis) of the (B) deformed cross-section glass fiber is 1.3 to 10. Is preferable.
  • the ratio X / Y of the compounding weight X of (B) irregularly cross-sectional glass fiber to 100 parts by weight of the (A) polyphenylene sulfide resin and (C) compounding weight Y of non-fiber inorganic filler Is more than 1 and less than 5.
  • the (C) non-fiber-based inorganic filler described above is calcium carbonate.
  • the molded product of the present invention it is preferable that the molded product is a housing component.
  • the present invention can provide a polyphenylene sulfide resin composition and a molded product thereof, which are excellent in mechanical properties and dimensional stability, particularly in which anisotropy is significantly suppressed and expansion during wet heat treatment is suppressed.
  • the (A) PPS resin used in the present invention is a polymer having a repeating unit represented by the following structural formula, and from the viewpoint of heat resistance, the repeating unit represented by the above structural formula is 70 mol% or more, further 90. A polymer containing mol% or more is preferable.
  • the repeating unit of the PPS resin may be composed of a repeating unit having the following structure or the like.
  • the method for producing the PPS resin used in the present invention will be described below. First, the contents of the polyhalogenated aromatic compound, the sulfide agent, the polymerization solvent, the molecular weight modifier, the polymerization aid and the polymerization stabilizer to be used will be described.
  • the polyhalogenated aromatic compound is a compound having two or more halogen atoms in one molecule. Specific examples include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, and hexa.
  • Polyhalogenated fragrances such as chlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 1-methoxy-2,5-dichlorobenzene Group compounds are mentioned, and p-dichlorobenzene is preferably used. It is also possible to combine two or more different polyhalogenated aromatic compounds to form a copolymer, but it is preferable that the p-dihalogenated aromatic compound is the main component.
  • the amount of the polyhalogenated aromatic compound used is 0.9 to 2.0 mol, preferably 0.95 to 1.5 mol, per mol of the sulfidizing agent, from the viewpoint of obtaining a PPS resin having a viscosity suitable for processing. More preferably, the range of 1.005 to 1.2 mol can be exemplified.
  • sulfidizing agent examples include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfides.
  • alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures of two or more of these, and sodium sulfide is preferably used.
  • These alkali metal sulfides can be used as hydrates or aqueous mixtures, or in the form of anhydrides.
  • alkali metal hydrosulfide examples include sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and a mixture of two or more of these, among which sodium hydrosulfide is used. It is preferably used.
  • These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures, or in the form of anhydrides.
  • a sulfidizing agent prepared in situ in the reaction system from alkali metal hydrosulfide and alkali metal hydroxide can also be used. Further, a sulfidizing agent can be prepared from alkali metal hydrosulfide and alkali metal hydroxide, and this can be transferred to a polymerization tank for use.
  • a sulfidizing agent prepared in situ in the reaction system from alkali metal hydroxides such as lithium hydroxide and sodium hydroxide and hydrogen sulfide can also be used.
  • a sulfidizing agent can be prepared from alkali metal hydroxides such as lithium hydroxide and sodium hydroxide and hydrogen sulfide, and this can be transferred to a polymerization tank for use.
  • the amount of the charged sulfidating agent shall mean the residual amount obtained by subtracting the lost amount from the actual charged amount when a partial loss of the sulfidizing agent occurs before the start of the polymerization reaction due to a dehydration operation or the like.
  • alkali metal hydroxide and / or an alkaline earth metal hydroxide in combination with the sulfidizing agent.
  • alkali metal hydroxide include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide and a mixture of two or more of these, and alkaline earth.
  • metal hydroxide include calcium hydroxide, strontium hydroxide, barium hydroxide and the like, and sodium hydroxide is preferably used.
  • alkali metal hydrosulfide When alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use alkali metal hydroxide at the same time, but the amount used is 0.95 to 1. per 1 mol of alkali metal hydrosulfide.
  • An example is in the range of 20 mol, preferably 1.00 to 1.15 mol, more preferably 1.005 to 1.100 mol.
  • N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone
  • caprolactams such as N-methyl- ⁇ -caprolactam
  • 1,3-dimethyl-2-imidazolidi examples thereof include aprotic organic solvents typified by non-, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphate triamide, dimethylsulfone, tetramethylenesulfoxide, and mixtures thereof, all of which are used. It is preferably used because of its high reaction stability.
  • NMP N-methyl-2-pyrrolidone (hereinafter, may be abbreviated as NMP) is particularly preferably used.
  • the amount of the organic polar solvent used is selected in the range of 2.0 to 10 mol, preferably 2.25 to 6.0 mol, more preferably 2.5 to 5.5 mol, per 1 mol of the sulfidizing agent. ..
  • a monohalogenated compound (not necessarily an aromatic compound) is used in combination with the polyhalogenated aromatic compound in order to form the terminal of the PPS resin to be produced, or to adjust the polymerization reaction or molecular weight. be able to.
  • polymerization aid it is also one of the preferable embodiments to use a polymerization aid in order to obtain a PPS resin having a relatively high degree of polymerization in a shorter time.
  • the polymerization aid means a substance having an action of increasing the viscosity of the obtained PPS resin.
  • Specific examples of such polymerization aids include, for example, organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates and alkaline soils. Examples include metal phosphates. These can be used alone or in combination of two or more. Of these, organic carboxylates and / or water are preferably used.
  • the alkali metal carboxylate is a general formula R (COMM) n (in the formula, R is an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group having 1 to 20 carbon atoms.
  • M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium.
  • N is an integer of 1).
  • Alkali metal carboxylates can also be used as hydrates, anhydrides or aqueous solutions. Specific examples of the alkali metal carboxylate include lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluic acid, and mixtures thereof. Can be mentioned.
  • the alkali metal carboxylate is a reaction in which an organic acid and one or more compounds selected from the group consisting of alkali metal hydroxide, alkali metal carbonate and alkali metal bicarbonate are added in approximately equal chemical equivalents and reacted. It may be formed by.
  • the lithium salt has high solubility in the reaction system and has a large auxiliary effect, but is expensive, and the potassium, rubidium and cesium salts have insufficient solubility in the reaction system. Therefore, sodium acetate, which is inexpensive and has an appropriate solubility in a polymerization system, is most preferably used.
  • the amount used is usually in the range of 0.01 mol to 0.7 mol with respect to 1 mol of the charged alkali metal sulfide, and is 0.1 to 0.1 in the sense of obtaining a higher degree of polymerization.
  • the range of 0.6 mol is preferable, and the range of 0.2 to 0.5 mol is more preferable.
  • water as a polymerization aid is one of the effective means for obtaining a resin composition in which fluidity and high toughness are highly balanced.
  • the amount to be added is usually in the range of 0.5 mol to 15 mol with respect to 1 mol of the charged alkali metal sulfide, and is preferably in the range of 0.6 to 10 mol in order to obtain a higher degree of polymerization. The range of 1 to 5 mol is more preferable.
  • the timing of addition of these polymerization aids is not particularly specified, and may be added at any time of the pre-process, the start of polymerization, and the middle of polymerization, which will be described later, or may be added in a plurality of times.
  • an alkali metal carboxylate used as the polymerization aid, it is more preferable to add it at the same time as the start of the previous step or the start of polymerization because it is easy to add.
  • water is used as a polymerization aid, it is effective to add the polyhalogenated aromatic compound in the middle of the polymerization reaction after charging it.
  • a polymerization stabilizer can also be used to stabilize the polymerization reaction system and prevent side reactions.
  • the polymerization stabilizer contributes to the stabilization of the polymerization reaction system and suppresses unwanted side reactions.
  • One guideline for the side reaction is the production of thiophenol, and the production of thiophenol can be suppressed by adding a polymerization stabilizer.
  • Specific examples of the polymerization stabilizer include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, and alkaline earth metal carbonates. Among them, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferable.
  • the above-mentioned alkali metal carboxylate also acts as a polymerization stabilizer, it is one of the polymerization stabilizers used in the present invention. Further, when an alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use the alkali metal hydroxide at the same time, but here, the alkali metal water which is excessive with respect to the sulfidizing agent. Oxides can also be polymerization stabilizers.
  • the ratio of the polymerization stabilizer to 1 mol of the charged alkali metal sulfide is usually 0.02 to 0.2 mol, preferably 0.03 to 0.1 mol, and more preferably 0.04 to 0.09 mol. It is preferable to use in. At this preferable ratio, the stabilizing effect is sufficient, while the polymer yield is excellent.
  • the timing of addition of the polymerization stabilizer is not particularly specified, and it may be added at any time of the pre-process, the start of polymerization, and the middle of polymerization, which will be described later, or it may be added in a plurality of times. It is more preferable to add at the same time at the start of the process or the start of polymerization.
  • the sulfidizing agent is usually used in the form of a hydrate, but before adding the polyhalogenated aromatic compound, the mixture containing the organic polar solvent and the sulfidizing agent is heated to remove an excess amount of water. It is preferable to remove it. If too much water is removed by this operation, it is preferable to add the insufficient water to replenish the water.
  • an alkali metal sulfide prepared from alkali metal hydrosulfide and alkali metal hydroxide in situ in the reaction system or in a tank separate from the polymerization tank is also used. be able to.
  • This method is not particularly limited, but preferably in an inert gas atmosphere, in a temperature range of room temperature to 150 ° C., preferably room temperature to 100 ° C., alkali metal hydrosulfide and alkali metal hydroxide are used as organic polar solvents.
  • the temperature is raised to at least 150 ° C. or higher, preferably 180 to 245 ° C. under normal pressure or reduced pressure to distill off water.
  • a polymerization aid may be added at this stage.
  • toluene or the like may be added to carry out the reaction.
  • the amount of water in the polymerization system in the polymerization reaction is preferably 0.5 to 10.0 mol per mol of the charged sulfidizing agent.
  • the amount of water in the polymerization system is the amount obtained by subtracting the amount of water removed from the polymerization system from the amount of water charged in the polymerization system.
  • the water to be charged may be in any form such as water, an aqueous solution, and water of crystallization.
  • Polymerization reaction step It is preferable to produce PPS resin powder or granular material by reacting a sulfidizing agent and a polyhalogenated aromatic compound in an organic polar solvent within a temperature range of 200 ° C. or higher and lower than 290 ° C.
  • a sulfidizing agent and a polyhalogenated aromatic compound are added to the organic polar solvent in a temperature range of preferably normal temperature to 215 ° C., preferably 100 to 215 ° C. in an inert gas atmosphere.
  • a polymerization aid may be added at this stage.
  • the order in which these raw materials are charged may be random or simultaneous.
  • the temperature of such a mixture is usually raised to the range of 200 ° C to 290 ° C.
  • the rate of temperature rise is not particularly limited, but usually a rate of 0.01 to 5 ° C./min is selected, and a range of 0.1 to 3 ° C./min is more preferable.
  • the temperature is finally raised to a temperature of 250 to 290 ° C., and the reaction is carried out at that temperature for usually 0.25 to 50 hours, preferably 0.5 to 20 hours.
  • a method of reacting at 200 ° C. to 245 ° C. for a certain period of time and then raising the temperature to 270 to 290 ° C. before reaching the final temperature is effective in obtaining a higher degree of polymerization.
  • the reaction time at 200 ° C. to 245 ° C. is usually selected in the range of 0.25 to 20 hours, preferably in the range of 0.25 to 10 hours.
  • the most preferable recovery method of the PPS resin is to carry out under quenching conditions, and one preferred method of this recovery method is the flash method.
  • the flash method the polymerization reaction product is flushed from a high temperature and high pressure (usually 250 ° C. or higher, 8 kg / cm 2 or higher) into an atmosphere of normal pressure or reduced pressure, and the polymer is made into powder or granular material at the same time as the solvent is recovered.
  • This is a recovery method
  • flash as used herein means that the polymerization reaction product is ejected from the nozzle.
  • Specific examples of the flashing atmosphere include nitrogen or water vapor under normal pressure, and the temperature is usually selected in the range of 150 ° C. to 250 ° C.
  • the flash method is an economical recovery method because the solid matter can be recovered at the same time as the solvent is recovered and the recovery time can be relatively short.
  • ionic compounds typified by Na and organic low-degree-of-polymerization products (oligomers) tend to be easily incorporated into the polymer during the solidification process.
  • the method for recovering the PPS resin used in the present invention is not limited to the flash method. As long as the method satisfies the requirements of the present invention, a method of slowly cooling to recover the particulate polymer (quenching method) may be used. However, from the viewpoint of economy and performance, it is more preferable to use the PPS resin recovered by the flash method in the production method of the present invention.
  • a PPS resin that has undergone the above-mentioned polymerization reaction step and recovery step and then undergoes thermal oxidation treatment. It is preferable to include hot water treatment and acid treatment before the thermal oxidation treatment step. Further, a step of washing with an organic solvent may be included before the step of acid treatment or the step of hot water treatment.
  • the acid used for the acid treatment in the present invention is not particularly limited as long as it does not have an action of decomposing the PPS resin, and examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid.
  • Acetic acid and hydrochloric acid are more preferably used, but those that decompose and deteriorate PPS resins such as nitric acid are not preferable.
  • the water is preferably distilled water or deionized water.
  • the aqueous acid solution preferably has a pH of 1 to 7, more preferably pH 2 to 4. When the pH is 7 or less, the metal content of the PPS resin does not increase, and when the pH is 1 or more, the volatile components of the PPS resin do not increase.
  • the temperature at the time of heating is preferably 80 to 250 ° C, more preferably 120 to 200 ° C, and even more preferably 150 to 200 ° C.
  • the temperature at the time of heating is 80 ° C. or higher, the acid treatment effect is sufficient, the metal content does not increase, and when the temperature is 250 ° C. or lower, the pressure does not become too high, which is preferable for safety.
  • the pH when the PPS resin is immersed in an aqueous acid solution for treatment is preferably 8 or less by the acid treatment, and more preferably pH 2 to 8. When the pH is 8 or less, the metal content of the obtained PPS resin does not increase.
  • the acid treatment time is preferably a time during which the reaction between the PPS resin and the acid is sufficiently equilibrated, preferably 2 to 24 hours when treated at 80 ° C., and 0.01 to 5 hours when treated at 200 ° C. preferable.
  • the ratio of the PPS resin to the acid or the aqueous solution of the acid in the acid treatment is preferably treated in a state where the PPS resin is sufficiently immersed in the acid or the aqueous solution of the acid, and 500 g of the PPS resin is treated with the acid or the acid.
  • the aqueous solution is preferably 0.5 to 500 L, more preferably 1 to 100 L, and even more preferably 2.5 to 20 L.
  • the acid or the aqueous solution of the acid is 0.5 L or more with respect to 500 g of the PPS resin, the PPS resin is sufficiently immersed in the aqueous solution, so that the washing is sufficient and the metal content of the PPS resin does not increase.
  • the acid or the aqueous solution of the acid is 500 L or less with respect to 500 g of the PPS resin, the amount of the solution to the PPS resin is appropriate and the production efficiency is good.
  • These acid treatments are performed by adding a predetermined amount of PPS resin to a predetermined amount of water and acid, heating and stirring in a pressure vessel, and continuously performing acid treatment.
  • a method for separating the aqueous solution and the PPS resin from the treated solution after the acid treatment filtration using a sieve or a filter is convenient, and methods such as natural filtration, pressure filtration, vacuum filtration, and centrifugal filtration can be exemplified.
  • Examples of the cleaning method include a method of filtering the PPS resin on the filtration device while sprinkling water on it, and a method of separating the aqueous solution and the PPS resin by adding the separated PPS resin to the water prepared in advance and then filtering again. it can.
  • the water used for washing is preferably distilled water or deionized water.
  • the water used for the hot water treatment in the present invention is preferably distilled water or deionized water.
  • the hot water treatment temperature is preferably 80 to 250 ° C., more preferably 120 to 200 ° C., and even more preferably 150 to 200 ° C.
  • the hot water treatment temperature is 80 ° C. or higher, the hot water treatment effect is sufficient, the amount of volatile gas generated is small, and when the hot water treatment temperature is 250 ° C. or lower, the pressure does not become too high, which is preferable for safety.
  • the hot water treatment time is preferably a time when the extraction treatment with PPS resin and hot water is sufficient, preferably 2 to 24 hours when the treatment is performed at 80 ° C., and 0.01 to 5 hours when the treatment is performed at 200 ° C. Is preferable.
  • the ratio of PPS resin to water in the hot water treatment is preferably treated in a state where the PPS resin is sufficiently immersed in water, preferably 0.5 to 500 L of water with respect to 500 g of PPS resin, and 1 to 100 L. Is more preferable, and 2.5 to 20 L is further preferable. If the amount of water is 0.5 L or more with respect to 500 g of the PPS resin, the PPS resin is sufficiently immersed in the water, so that the cleaning is sufficient and the amount of volatile gas generated does not increase. Further, when the amount of water is 500 L or less with respect to 500 g of the PPS resin, the ratio of water to the PPS resin is appropriate and the production efficiency is good.
  • the operation of these hot water treatments is not particularly limited, and is carried out by a method of adding a predetermined amount of PPS resin to a predetermined amount of water, heating and stirring in a pressure vessel, a method of continuously performing hot water treatment, and the like. ..
  • There is no particular limitation on the method of separating the aqueous solution and the PPS resin from the treated solution after hot water treatment but filtration using a sieve or a filter is convenient, and methods such as natural filtration, pressure filtration, vacuum filtration, and centrifugal filtration are available. Can be exemplified.
  • the cleaning method is not particularly limited, but the aqueous solution and the PPS resin can be filtered by sprinkling water on the PPS resin on the filtration device, or by adding the separated PPS resin to the water prepared in advance and then filtering again.
  • the method of separating the above can be exemplified.
  • the water used for washing is preferably distilled water or deionized water.
  • the acid treatments and hot water treatments are carried out in an inert atmosphere.
  • the inert atmosphere include nitrogen, helium, and argon, but a nitrogen atmosphere is preferable from the viewpoint of economy.
  • the present invention may include a step of washing with an organic solvent before the step of acid treatment or the step of hot water treatment, and the method is as follows.
  • the organic solvent used for cleaning the PPS resin in the present invention is not particularly limited as long as it does not have an action of decomposing the PPS resin.
  • N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, 1,3 -Nitrogen-containing polar solvents such as dimethylimidazolidinone, hexamethylphosphorasamide and piperazinones, sulfoxide-sulfone solvents such as dimethylsulfoxide, dimethylsulfone and sulfolane, ketone solvents such as acetone, methylethylketone, diethylketone and acetophenone, Ether-based solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, halogen-based solvents such as chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrachloroethane, perchlorethane, and chlorobenzene.
  • polar solvents such as dimethyl
  • organic solvents the use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferable.
  • these organic solvents are used in one kind or a mixture of two or more kinds.
  • the cleaning temperature when cleaning the PPS resin with an organic solvent is not particularly limited, and any temperature of about room temperature to 300 ° C. can be selected. The higher the cleaning temperature, the higher the cleaning efficiency tends to be, but usually, a sufficient effect can be obtained at a cleaning temperature of room temperature to 150 ° C. It is also possible to wash under pressure in a pressure vessel at a temperature higher than the boiling point of the organic solvent. In addition, there is no particular limitation on the cleaning time. Although it depends on the cleaning conditions, in the case of batch-type cleaning, a sufficient effect is usually obtained by cleaning for 5 minutes or more. It is also possible to wash continuously.
  • the PPS resin used in the present invention is preferably one obtained by undergoing thermal oxidation treatment after the above acid treatment, hot water treatment or washing with an organic solvent.
  • the thermal oxidation treatment referred to here is a treatment by heating the PPS resin in an oxygen atmosphere or by adding a peroxide such as H 2 O 2 or a vulcanizing agent such as S.
  • a peroxide such as H 2 O 2
  • a vulcanizing agent such as S.
  • heating in an oxygen atmosphere is particularly preferable because of the ease of treatment.
  • the heating device for the thermal oxidation treatment of the PPS resin may be a normal hot air dryer, a rotary type or a heating device with a stirring blade, but in the case of efficient and more uniform treatment, It is more preferable to use a heating device of a rotary type or a stirring blade. It is desirable that the oxygen concentration in the atmosphere during the thermal oxidation treatment is 1% by volume or more, more preferably 2% by volume or more. In order to exert the effect of the present invention, the upper limit of the oxygen concentration is preferably 5% by volume or less.
  • the thermal oxidation treatment By performing the thermal oxidation treatment at an oxygen concentration of 5% by volume or less, the thermal oxidation treatment does not proceed excessively, and the toughness of the molded product containing the PPS resin subjected to the thermal oxidation treatment is not impaired. On the other hand, it is preferable to perform the thermal oxidation treatment at an oxygen concentration of 1% by volume or more because a sufficient thermal oxidation treatment can be performed and a PPS resin having a small amount of volatile components can be obtained.
  • the thermal oxidation treatment temperature of the PPS resin is preferably 160 to 270 ° C, more preferably 160 to 230 ° C. It is preferable to carry out the thermal oxidation treatment at 270 ° C. or lower because the thermal oxidation treatment does not proceed rapidly and the toughness of the molded product containing the PPS resin subjected to the thermal oxidation treatment is not impaired. On the other hand, by performing the thermal oxidation treatment at a temperature of 160 ° C. or higher, the thermal oxidation treatment can proceed at an appropriate speed, and a PPS resin with a small amount of volatile components generated can be obtained, which is preferable.
  • the treatment time of the thermal oxidation treatment is preferably 0.5 to 30 hours, more preferably 0.5 to 25 hours, and even more preferably 2 to 20 hours. It is preferable that the treatment time is 0.5 hours or more because sufficient thermal oxidation treatment can be performed and a PPS resin having a small amount of volatile components can be obtained. By setting the treatment time to 30 hours or less, the cross-linking reaction by the thermal oxidation treatment can be controlled, and the toughness of the molded product containing the PPS resin subjected to the thermal oxidation treatment is not impaired, which is preferable.
  • the PPS resin used in the present invention preferably has a gas generation amount of 0.3% by weight or less when it is heated and melted at 320 ° C. for 2 hours under vacuum.
  • the amount of gas generated is 0.3% by weight or less, the volatile components adhering to the mold and the mold vent portion do not increase, and transfer failure and gas burning are unlikely to occur.
  • the lower limit of the amount of gas generated is not particularly limited, but it is economically disadvantageous if the time required for polymer cleaning or thermal oxidation treatment, which is mentioned as a method for reducing the amount of gas generated, becomes long.
  • the amount of gas generated means the amount of the adhesive component in which the gas volatilized when the PPS resin is heated and melted under vacuum is cooled and liquefied or solidified, and the glass in which the PPS resin is vacuum-sealed.
  • the ampoule is measured by heating it in a tubular furnace.
  • As the shape of the glass ampoule one having an abdomen of 100 mm ⁇ 25 mm, a neck of 255 mm ⁇ 12 mm, and a wall thickness of 1 mm is used.
  • As a specific measurement method only the body of a glass ampoule vacuum-sealed with PPS resin is inserted into a tube furnace at 320 ° C.
  • the ampoule is volatile at the neck of the ampoule that is not heated by the tube furnace.
  • the gas is cooled and adheres. After cutting out the neck and weighing it, the attached gas is dissolved in chloroform and removed. The neck is then dried and then weighed again. The amount of gas generated is calculated from the weight difference between the ampoule necks before and after the gas is removed.
  • the melt flow rate (hereinafter, sometimes abbreviated as MFR) of the PPS resin obtained through the above-mentioned pre-step, polymerization reaction step, recovery step, preferably washing step, and heat treatment step is 1000 g / 10 minutes or more. It is preferably 1500 g / 10 minutes or more, and more preferably 3000 g / 10 minutes or more.
  • MFR is 1500 g / 10 minutes or more, the fluidity is excellent and the moldability is good.
  • MFR is a value measured according to ASTM-D1238-70 at a measurement temperature of 315.5 ° C. and a load of 5000 g.
  • the PPS resin used in the present invention preferably has an ash content of 0.3% by weight or less when incinerated at 550 ° C.
  • the ash content is 0.3% by weight or less, it means that the metal content of the PPS resin is appropriately low.
  • the metal content is appropriately low, the electrical insulation is excellent, the melt fluidity is good, and the moisture and heat resistance is also excellent.
  • the PPS resin used in the present invention is dissolved in 1-chloronaphthalene having a weight of 20 times at 250 ° C. for 5 minutes, and the amount of residue when hot pressure filtration is performed with a PTFE membrane filter having a pore size of 1 ⁇ m is 4.0 weight by weight. % Or less is preferable.
  • the amount of the residue is 4.0% by weight or less, it means that the thermal oxidation cross-linking of the PPS resin does not proceed excessively and the gelled product in the resin is appropriately small.
  • the thermal oxidation cross-linking of the PPS resin is prevented from proceeding excessively, the toughness of the PPS resin is kept good and the mechanical strength is excellent.
  • the lower limit of the residual amount is not particularly limited, but is 1.5% by weight or more, preferably 1.7% by weight or more. If the amount of the residue is less than 1.5% by weight, the degree of thermal oxidation cross-linking is too slight, so that the volatile components at the time of melting are not so reduced, and the effect of reducing the volatile content may be small.
  • the PPS resin composition of the present invention comprises 100 parts by weight of (A) polyphenylene sulfide resin and 100 to 250 parts by weight of (B) irregularly shaped cross-section glass fiber.
  • the (B) modified cross-section glass fiber of the present invention is a glass fiber having a flat cross section (hereinafter, may be abbreviated as flat glass fiber), and has a major axis in the cross section when the glass fiber is cut at a right angle in the length direction.
  • the ratio of (the longest linear distance in the cross section) to the minor axis (the longest linear distance in the direction perpendicular to the major axis) (hereinafter sometimes abbreviated as flatness) is preferably 1.3 to 10. It is preferably 1.5 to 7, and more preferably 1.5 to 5.
  • the flatness is 1.3 or more, the resin composition has good toughness and dimensional accuracy, and when it is 10 or less, the resin composition has good strength.
  • the major axis of the cross section of the flat glass fiber is preferably 10 to 80 ⁇ m, which facilitates spinning of the glass fiber and maintains high strength of the glass fiber. More preferably, it is 15 ⁇ m or more and 50 ⁇ m or less.
  • the minor axis of the cross section is preferably 2 to 20 ⁇ m, more preferably 4 ⁇ m or more and 15 ⁇ m or less.
  • the major axis / minor axis ratio (flatness) of the glass fiber cross section was observed with a scanning electron microscope, and the major axis and minor axis of the cross section of 50 randomly selected glass fibers were measured and the ratio was measured. It is a value obtained by calculating and calculating the number average.
  • Flat glass fiber has a larger specific surface area than glass fiber having a circular cross-sectional shape with the same cross-sectional area.
  • the glass fibers are easily oriented in the flow direction of the molded product, there is less collision between the glass fibers during molding, and breakage is further suppressed.
  • the orientation further reduces the anisotropy of the molded product.
  • the anisotropy described here is the difference in the coefficient of linear expansion in the resin flow direction (MD direction) and the direction perpendicular to the flow direction (TD direction) in a test piece having a thickness of 80 mm ⁇ 80 mm ⁇ 3 mm, and the square plate thereof.
  • Creep deformation refers to the plastic deformation amount obtained by subtracting the elastic deformation amount from the total deformation amount in the tensile creep deformation.
  • the small anisotropy means that the difference in various characteristics such as the coefficient of linear expansion and creep deformation is small in the TD direction and the MD direction.
  • the blending amount of the (B) modified cross-section glass fiber used in the present invention is 100 to 250 parts by weight with respect to 100 parts by weight of the above (A) polyphenylene sulfide resin. If the amount of (B) irregularly shaped cross-section glass fiber is less than 100 parts by weight with respect to 100 parts by weight of (A) polyphenylene sulfide resin, a difference due to anisotropy occurs. It is preferably 110 parts by weight or more. If the amount of (B) modified cross-section glass fiber exceeds 250 weight with respect to 100 parts by weight of (A) polyphenylene sulfide resin, the fluidity is impaired and the moldability is affected. It is preferably 220 parts by weight or less.
  • the polyphenylene sulfide resin composition of the present invention comprises (A) a polyphenylene sulfide resin mixed with (C) 25 to 150 parts by weight of a non-fiber-based inorganic filler.
  • the non-fiber-based inorganic filler (C) is characterized by satisfying the following (Ca) and (Cb).
  • (Ca) Mohs hardness is more than 2 and less than 4
  • (Cb) Melting point or softening point is 380 ° C. or more
  • the above Mohs hardness means 10-step Mohs hardness. When the Mohs hardness is 2 or less, deformation occurs due to the irregular cross-section glass that is kneaded at the same time, and the dimensional stability deteriorates. Further, when it is 4 or more, the wear of the processing jig such as a molding machine is promoted.
  • the preferred Mohs hardness is greater than 2.5 and less than 4.
  • the Mohs hardness is the value of the Mohs hardness measured in a lump state to some extent before the shape (granular) used as the non-fiber-based inorganic filler is set to "(C) Non-fiber-based inorganic filler. Mohs hardness of.
  • the processing temperature of the PPS resin is 300 to 340 ° C, and the resin temperature may reach 380 ° C or higher due to the application of shearing force to the resin. Therefore, since the non-fiber-based inorganic filler that contributes to dimensional stability is required to have shape stability even at the processing temperature, (C) the non-fiber-based inorganic filler may have a melting point or a softening point of 380 ° C. or higher. It is necessary and preferably has a melting point or softening point of 400 ° C. or higher. The upper limit of the melting point or the softening point is not particularly defined, but is about 2,000 ° C. as a practical type of non-fiber-based inorganic filler. Here, the melting point or softening point is defined by a value measured using differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • a non-fibrous filler such as a carbonate such as mica, calcium carbonate, magnesium carbonate or dolomite, or a sulfate such as calcium sulfate or barium sulfate is used. These may be hollow, and two or more kinds of these non-fiber-based inorganic fillers can be used in combination. Further, these non-fiber inorganic fillers may be pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound and an epoxy compound before use.
  • a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound and an epoxy compound before use.
  • At least one selected from mica and calcium carbonate is preferable from the viewpoint of reducing the thermal expansion of the material, and calcium carbonate is preferable from the viewpoint of reducing anisotropy.
  • the (C) non-fiber-based inorganic filler of the present invention excludes hexagonal boron nitride, magnesium hydroxide, talc, magnesium oxide, and aluminum nitride.
  • the blending amount of (C) non-fiber-based inorganic filler in the PPS resin composition of the present invention is preferably 25 to 150 parts by weight of (C) non-fiber-based inorganic filler with respect to 100 parts by weight of (A) PPS resin. Is 30 parts by weight to 130 parts by weight.
  • the ratio X / Y of (B) the compounding weight X of the modified cross-section glass fiber to (C) the compounding weight Y of the non-fiber-based inorganic filler with respect to 100 parts by weight of the polyphenylene sulfide resin is larger than 1 and 7 Is less than. It is preferably greater than 1 and less than 5.
  • the ratio X / Y is 1 or less, that is, the compounding weight of (B) the modified cross-sectional glass fiber and (C) the non-fiber-based inorganic filler is the same, or (B) the compounding weight of the modified cross-sectional glass fiber is (B). C) If it is less than the blending weight of the non-fiber-based inorganic filler, the anisotropy of the molded product cannot be controlled, and the dimensional change during moist heat expansion becomes significantly large.
  • the ratio X / Y is 7 or more, that is, when (B) the blended weight of the irregular cross-section glass fiber is very large and (C) the blended weight of the non-fiber-based inorganic filler is small, the influence of the irregular cross-section glass is strong. As a result, the coefficient of linear expansion increases and the low anisotropy is lost.
  • the PPS resin composition of the present invention has at least one selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group and a ureido group for the purpose of improving mechanical strength and toughness. It is preferable to add an alkoxysilane compound having a functional group. Specific examples of such compounds include epoxy group-containing alkoxysilane compounds such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • ⁇ -Mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxysilane and other mercapto group-containing alkoxysilane compounds ⁇ -ureidopropyltriethoxysilane, ⁇ -ureidopropyltrimethoxysilane, ⁇ - (2-ureidoethyl) amino Ureid group-containing alkoxysilane compounds such as propyltrimethoxysilane, ⁇ -isocyanatepropyltriethoxysilane, ⁇ -isocyanatepropyltrimethoxysilane, ⁇ -isocyanatepropylmethyldimethoxysilane, ⁇ -isocyanatepropylmethyldiethoxysilane, ⁇ -isocyanatepropyl Isocyanate group-containing alkoxysilane compounds such as ethyldimethoxysilane, ⁇ -isocyanatepropylethy
  • alkoxysilane compounds examples thereof include alkoxysilane compounds.
  • an alkoxysilane having an epoxy group, an amino group, an isocyanate group, and a hydroxyl group is particularly suitable for obtaining excellent weld strength.
  • a suitable amount of the silane compound added is selected in the range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the (A) PPS resin.
  • the PPS resin composition of the present invention is further blended with a resin other than (D) (A) PPS resin (hereinafter, may be abbreviated as (D) other resin) as long as the effect of the present invention is not impaired. May be used.
  • the blendable resin is not particularly limited, and specific examples thereof include polyamides such as nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, and aromatic nylon, polyethylene terephthalate, polybutylene terephthalate, and poly.
  • Polyester resins such as cyclohexyldimethylene terephthalate and polynaphthalene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene, polyolefin-based elastomers, polyether ester elastomers, polyetheramide elastomers, polyamideimides, polyacetals, polyimides, polyphenylene ethers, polyetherimides, Polyether sulfone, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyether ketone resin, polythioether ketone resin, polyether ether ketone resin, polyamideimide resin, tetrafluoride polyethylene resin, epoxy
  • Examples thereof include a group-containing polyolefin copolymer, a bisphenol epoxy resin such as bisphenol A type, a novolak phenol type epoxy resin, and a cresol novolak type epoxy resin.
  • polyimide, polyphenylene ether, polyetherimide, and polyether sulfone are desirable for the purpose of suppressing thermal deformation of the PPS resin at a glass transition temperature (about 80 ° C.) or higher.
  • a suitable amount of the (D) other resin added is selected in the range of 0 to 20 parts by weight with respect to 100 parts by weight of the (A) PPS resin.
  • the PPS resin composition of the present invention contains other components, such as antioxidants, heat-resistant stabilizers (hydroquinone-based), and weather-resistant agents (resorcinol-based, salicylate-based), as long as the effects of the present invention are not impaired.
  • Bentriazole-based, benzophenone-based, hindered amine-based, etc.), antistatic agents and lubricants (montanic acid and its metal salts, their esters, their half esters, stearic acid, stearamide, bisurea and polyethylene wax, etc.), pigments (cadmium sulfide, Phthalocyanin, carbon black for coloring, etc.), dyes (niglosin, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agents (alkylsulfate-type anionic antistatic agents, quaternary ammonium Salt-type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents, etc.), flame retardants (eg, red phosphorus, phosphate ester, melamine cyanurate, polyphosphorus) Ammonium acid, brominated polys
  • the method for preparing the PPS resin composition of the present invention is not particularly limited, but each raw material is supplied to a commonly known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader and a mixing roll, and 280.
  • a typical example is a method of kneading at a temperature of about 380 ° C.
  • the mixing order of the raw materials is not particularly limited, and all the raw materials are blended and then melt-kneaded by the above method, some raw materials are blended and then melt-kneaded by the above method, and the remaining raw materials are blended and melt-kneaded.
  • Any method may be used, such as a method of mixing some raw materials and then mixing the remaining raw materials using a side feeder during melt-kneading with a single-screw or twin-screw extruder.
  • a side feeder during melt-kneading with a single-screw or twin-screw extruder.
  • the small amount additive component it is of course possible to knead other components by the above method or the like to pelletize them, and then add them before molding and use them for molding.
  • MFR was calculated by the following method.
  • the polyphenylene sulfide resin was measured at a measurement temperature of 315.5 ° C. and a load of 345 g, ER was measured by a method according to ASTM-D1238-70, and the value of MFR was calculated by the following formula [I].
  • the piston was extruded and the solution was filtered through a membrane filter.
  • the membrane filter was taken out, vacuum dried at 150 ° C. for 1 hour, and then weighed. The difference in the weight of the membrane filter before and after filtration with respect to the charged weight of the pressed PPS was defined as the residual amount (% by weight).
  • the amount of residual water in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP.
  • the amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.
  • the obtained cake was dried at 120 ° C. under a nitrogen stream to obtain a dried PPS.
  • the obtained PPS had an ER of 90 g / 10 minutes, converted to MFR of 6257 g / 10 minutes, and a residual amount of 1.2% by weight.
  • PPS resin PPS PPS resin polymerized by the method described in the reference example
  • C Non-fiber-based inorganic filler C-1: Heavy calcium carbonate (KSS-1000 manufactured by Calfine Co., Ltd.), Mohs hardness: 3, melting point: 82 ° C.
  • compositions C-2 Talc (PK-S manufactured by Hayashi Kasei Co., Ltd.), Mohs hardness: 1, melting point:> 450 ° C (decomposition)
  • D Other resin
  • D-1 Polyether sulfone (manufactured by Sumitomo Chemical Co., Ltd., Sumika Excel 3600P)
  • D-2 Polyetherimide (manufactured by SABIC, Ultem 1010)
  • D-3 Polyphenylene ether (manufactured by Asahi Kasei Corporation, XYROS202A)
  • B' Fibrous filler (Comparative example: glass fiber not corresponding to the component (B) of the present invention)
  • B'-2 Chopped strand (manufactured by Nippon Electric Glass Co., Ltd., T-747H, average fiber diameter:
  • the measurement was performed according to ISO178 (2001). Specifically, the measurement was performed as follows.
  • the resin composition pellets are supplied to an injection molding machine (SE50DUZ-C160) manufactured by Sumitomo Heavy Industries, Ltd., which has a cylinder temperature of 310 ° C. and a mold temperature of 145 ° C., and is filled with a filling time of 0.8 s.
  • Injection molding was performed with a holding pressure of 75% to obtain a type B2 test piece shape specified in ISO 20753 (2008). This test piece was adjusted for 16 hours under the conditions of 23 ° C. and 50% relative humidity, and then measured under the conditions of 23 ° C. and 50% relative humidity, a span of 64 mm, and a strain rate of 2 mm / min. ..
  • the resin flow direction MD and the resin flow are measured from the cutting flat plate 4 for preparing a test piece, which is a square having a side SL of 80 mm and a thickness D of 3 mm shown in FIG.
  • a test piece having a width W of 5 mm, a length L of 10 mm, and a thickness D of 3 mm shown in FIG. 3 is cut out from the position shown in FIG. 2 by cutting with the TD in the direction perpendicular to the direction as the length direction.
  • the prepared test piece 5 and test piece 6 were used.
  • the flat plate 4 for cutting uses an injection molding machine NEX-1000-9E manufactured by Nissei Jushi Kogyo Co., Ltd., cylinder temperature: 320 ° C., injection pressure: lower limit molding pressure + 12.8 MPa, injection time: 15 sec, cooling time. : Made by injection molding under the condition of 15 sec.
  • FIG. 1A is a plan view of the cutting flat plate 4 for producing the test piece
  • FIG. 1B is a side view of the cutting flat plate 4 for creating the test piece.
  • the cutting flat plate 4 for producing the linear expansion coefficient test piece has a sprue 1, a runner 2, and a gate 3, and the test pieces 5 and 6 having the shape shown in FIG. 3 are cut at the positions shown in FIG. Made.
  • FIG. 3A is a plan view of the test pieces 5 and 6, and FIG. 3B is a side view of the test pieces 5 and 6.
  • the coefficient of linear expansion is TMA-100 manufactured by Seiko Electronics Co., Ltd., and the temperature range of -50 ° C to 200 ° C is raised at a rate of 5 ° C / min with a load load of 2 g, and the linear expansion coefficient is -40 ° C to 150 ° C. It was expressed numerically in the temperature range.
  • This test piece was treated for 1,000 hr in a high temperature and high humidity of 85 ° C. and 85% humidity, and then the expansion coefficient in the MD direction and the TD direction was measured.
  • the expansion coefficient is expressed by the following equation (2).
  • Expansion rate (%) [Post-processed dimensions (mm) -Initial dimensions (mm)] / Initial dimensions (mm) x 100 (2) The measurement position of the dimension was set to the center line in each MD direction and TD direction as shown by each arrow described in the cutting flat plate 4 of FIG.
  • the creep deformation evaluation of the PPS resin was carried out from the cutting flat plate 4 for making a test piece, which is a square with a side SL of 80 mm and a thickness D of 3 mm shown in FIG. 1, in the resin flow direction MD and the resin flow direction.
  • the TD is set in the perpendicular direction
  • the shape of the test piece described in JIS K 7161 (2014) is 1/2 of the shape of the test piece 1B so that the creep deformation evaluation test can be performed in each direction from the positions shown in FIGS.
  • a cut test piece was used for (half dumbbell).
  • This test piece was subjected to tensile creep treatment at a distance between grippers of 55 mm and a load of 12.5 MPa, and the elongation (plastic deformation) was measured from 1 minute to 40 hours after the start of the test.
  • the creep ratio is expressed by the following equation (3).
  • Creep ratio (%) plastic deformation in the MD direction (mm) / plastic deformation in the TD direction (mm) ⁇ 100 (3).
  • Examples 1 to 7 The PPS resin obtained in the reference example using a twin-screw extruder (TEM-26 manufactured by Toshiba Machine Co., Ltd.) having an intermediate addition port with a diameter of 26 mm, in which the cylinder temperature was set to 320 ° C. and the screw rotation speed was set to 400 rpm.
  • A) Non-fiber-based inorganic filler (C) and / or other resin (D) was added to 100 parts by weight from the raw material supply port at the weight ratio shown in Table 1 to bring it into a molten state, and
  • B a modified cross-sectional shape.
  • the PPS resin composition of the present invention has low linear expansion, low anisotropy, and low swelling property.
  • Comparative Example 1 had a large coefficient of linear expansion and anisotropy because it did not use glass fibers with a modified cross section. Furthermore, it was found that the swellability was also inferior because the ratio of the glass fiber to the non-fibrous filler was less than 1.
  • Comparative Examples 2 and 3 had a large coefficient of linear expansion and anisotropy because they did not use glass fibers having a modified cross section. On the other hand, it was found that the swellability was inferior because the ratio of the glass fiber to the non-fibrous filler was less than 1.
  • the PPS resin composition of the present invention can be used for various moldings such as injection molding, extrusion molding, blow molding, and transfer molding, but is particularly suitable for injection molding applications.
  • the PPS resin composition used in the present invention is excellent in low anisotropy in linear expansion coefficient and creep deformation without significantly impairing various physical properties such as inherent excellent mechanical properties and chemical resistance.
  • a PPS resin composition can be obtained. Therefore, it is useful for molded products that require dimensional accuracy and hold articles under contact pressure.
  • optical instruments and precision instruments that require optical characteristics are required to have dimensional stability and less anisotropy of creep deformation during lens press-fitting. Therefore, the resin composition of the present invention is used in these applications. Is very useful. Specific examples include applications in which lenses such as microscopes, binoculars, cameras, and watches are press-fitted.
  • PPS resin composition of the present invention include, for example, sensors, LED lamps, consumer connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, oscillators, and various terminal boards.
  • VTR parts TV parts, irons, hair dryers, rice cooker parts, microphone parts, acoustic parts, audio / laser discs (registered trademark)
  • Audio equipment parts such as compact discs, lighting parts, refrigerator parts, air conditioners It can also be applied to household and office electrical product parts such as parts, typewriter parts, and word processor parts.
  • Machine-related parts such as office computer-related parts, telephone equipment-related parts, facsimile-related parts, copying machine-related parts, cleaning jigs, motor parts, writers, typewriters, etc .
  • valves fuel-related / exhaust system / intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, Throttle position sensor, crank shaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, water pump housing, engine cooling module, turbine vane , Wiper motor related parts, Dustributor, Starter switch, Starter relay, Transmission wire harness, Window washer nozzle, Air conditioner panel switch board, Fuel related electromagnetic valve coil, Fuse connector, Horn terminal, Electrical component insulation plate, Step Various applications such as motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, vehicle speed sensors, cable liners, and other automobile / vehicle-related parts can be exemplified.

Abstract

[Problem] To provide a polyphenylene sulfide resin composition and a molded article thereof having excellent mechanical properties and dimensional stability, and particularly having significantly inhibited anisotropy and inhibited expansion during a moist heat treatment. [Solution] This polyphenylene sulfide resin composition is a mixture of (A) 100 parts by weight of a polyphenylene sulfide resin, (B) 100-250 parts by weight of atypical cross-section glass fibers, and (C) 25-150 parts by weight of a non-fiber inorganic filler satisfying (C-a) and (C-b), wherein the ratio X/Y of the mass X of the atypical cross-section glass fibers (B) and the mass Y of the non-fiber inorganic filler (C) is more than 1 but less than 7. (C-a) A Mohs hardness of more than 2 but less than 4. (C-b) A melting point or a softening point that is 380°C or higher.

Description

ポリフェニレンサルファイド樹脂組成物および成形品Polyphenylene sulfide resin composition and molded article
　本発明は、機械物性、および寸法安定性に優れ、特に異方性が大幅に抑制され、湿熱処理時の膨張が抑制されたポリフェニレンサルファイド樹脂組成物に関するものである。 The present invention relates to a polyphenylene sulfide resin composition which is excellent in mechanical properties and dimensional stability, particularly in which anisotropy is significantly suppressed and expansion during wet heat treatment is suppressed.
　ポリフェニレンサルファイド（以下、ＰＰＳと略す場合がある）樹脂は、耐熱性、難燃性、耐薬品性、電気絶縁性、耐湿熱性および機械的強度や寸法安定性に優れたエンジニアプラスチックであり、射出成形や押出成形などの各種成型法により、各種成型品や繊維、フィルムに成型可能であるため、電気・電子部品、機械部品および自動車部品など広範な分野において実用に供されている。 Polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin is an engineering plastic with excellent heat resistance, flame retardancy, chemical resistance, electrical insulation, moisture heat resistance, mechanical strength and dimensional stability, and is injection molded. Since it can be molded into various molded products, fibers, and films by various molding methods such as extrusion molding and extrusion molding, it is practically used in a wide range of fields such as electric / electronic parts, mechanical parts, and automobile parts.
　所望の特性を得る観点から、ＰＰＳ樹脂を繊維状無機充填材で強化したＰＰＳ樹脂組成物は、繊維状無機充填材の配向により熱による膨張、機械強度、および連続的な応力がかかった際の塑性変形量に関して、異方性が発現するため、金属と比較すると設計の自由度が低く、制限がかかることがあった。また、ＰＰＳ樹脂は低吸水性であるが、湿熱環境下においては湿熱膨張するため、当初の寸法を保持できないといった欠点もある。 From the viewpoint of obtaining desired properties, the PPS resin composition in which the PPS resin is reinforced with the fibrous inorganic filler is subjected to thermal expansion, mechanical strength, and continuous stress due to the orientation of the fibrous inorganic filler. Since anisotropy appears with respect to the amount of plastic deformation, the degree of freedom in design is lower than that of metal, and there are cases where restrictions are applied. Further, although the PPS resin has low water absorption, it has a drawback that it cannot maintain its original dimensions because it expands in a moist heat environment.
　近年、電子部品やカメラ部品などの精密部品は、機械的強度、難燃性に加えて、成形時のガス発生量が小さく（低ガス汚染性）、掛かる応力に対する塑性変形量が小さく、異方性がないこと（低異方性）が望まれ、さらに湿熱環境下における膨潤が小さいこと（低湿熱膨張）が求められている。 In recent years, precision parts such as electronic parts and camera parts have a small amount of gas generated during molding (low gas contamination) in addition to mechanical strength and flame retardancy, and a small amount of plastic deformation with respect to applied stress, which is anisotropic. It is desired that there is no property (low anisotropy), and that the swelling in a moist heat environment is small (low moist heat expansion).
　一般に、樹脂組成物の異方性を抑制する手法として、特許文献１、特許文献２および特許文献３のように扁平な断面形状を有するガラス繊維を充填することで、低異方性な熱可塑性樹脂組成物を提供することが知られている。 Generally, as a method for suppressing anisotropy of a resin composition, low anisotropy thermoplasticity is obtained by filling glass fibers having a flat cross-sectional shape as in Patent Document 1, Patent Document 2 and Patent Document 3. It is known to provide a resin composition.
特開２０１１－２６４３９号公報Japanese Unexamined Patent Publication No. 2011-26439 国際公開第２００８／０３８５１２号International Publication No. 2008/0385112 特表２０１６－５３５１４７号公報Special Table 2016-535147
　しかしながら、特許文献１では、成型収縮の異方性の改善が明示されているが、ポリカーボネートを使用しているため湿熱環境下での膨張が大きく、成形品の精密な寸法制御ができない。 However, although Patent Document 1 clearly states that the anisotropy of molding shrinkage is improved, since polycarbonate is used, the expansion in a moist heat environment is large, and precise dimensional control of the molded product cannot be performed.
　特許文献２および３でも、寸法安定性の改善が明示されているが、扁平を有するガラス繊維のみのため、温度変化時に、成形時の樹脂の流れ方向と流れに直角な方向とで膨張差が出てしまう。 Patent Documents 2 and 3 also clearly indicate the improvement in dimensional stability, but since only flat glass fibers are used, there is an expansion difference between the resin flow direction during molding and the direction perpendicular to the flow when the temperature changes. It will come out.
　そこで、本発明では、ＰＰＳ樹脂が本来有する優れた機械物性、耐薬品性などの諸物性を大きく損なうことなく、寸法安定性、および低異方性に優れ、湿熱処理時の膨潤が抑制されたＰＰＳ樹脂組成物を得ることを課題とする。 Therefore, in the present invention, the PPS resin is excellent in dimensional stability and low anisotropy without significantly impairing various physical properties such as mechanical properties and chemical resistance, and swelling during wet heat treatment is suppressed. An object of the present invention is to obtain a PPS resin composition.
　上記問題点を解決するために本発明のポリフェニレンサルファイド樹脂組成物は、以下の［１］、［２］のいずれかの構成を有する。すなわち、
［１］（Ａ）ポリフェニレンサルファイド樹脂１００重量部に対して、（Ｂ）異形断面ガラス繊維を１００～２５０重量部、および（Ｃ）以下の（Ｃ－ａ）および（Ｃ－ｂ）を満たす非繊維系無機フィラーを２５～１５０重量部配合してなるポリフェニレンサルファイド樹脂組成物であって、前記（Ｂ）異形断面ガラス繊維の配合重量Ｘと前記（Ｃ）非繊維系無機フィラーの配合重量Ｙとの比率Ｘ／Ｙが１より大きく７未満である、ポリフェニレンサルファイド樹脂組成物、
（Ｃ－ａ）モース硬度が２を超え４未満
（Ｃ－ｂ）融点もしくは軟化点が３８０℃以上
または、
［２］（Ａ）ポリフェニレンサルファイド樹脂１００重量部に対して、（Ｂ）異形断面ガラス繊維を１００～２５０重量部、および（Ｃ）非繊維系無機フィラー（但し、六方晶窒化ホウ素、水酸化マグネシウム、タルク、酸化マグネシウム、および窒化アルミニウムを除く）を２５～１５０重量部配合してなるポリフェニレンサルファイド樹脂組成物であって、 前記（Ｂ）異形断面ガラス繊維の配合重量Ｘと前記（Ｃ）非繊維系無機フィラーの配合重量Ｙとの比率Ｘ／Ｙが１より大きく７未満である、ポリフェニレンサルファイド樹脂組成物、である。 In order to solve the above problems, the polyphenylene sulfide resin composition of the present invention has any of the following configurations [1] and [2]. That is,
[1] For 100 parts by weight of (A) polyphenylene sulfide resin, 100 to 250 parts by weight of (B) irregularly shaped cross-sectional glass fiber, and (C) non-satisfying (Ca) and (Cb) below. A polyphenylene sulfide resin composition obtained by blending 25 to 150 parts by weight of a fiber-based inorganic filler, wherein the blended weight X of the (B) modified cross-sectional glass fiber and the blended weight Y of the (C) non-fiber-based inorganic filler are used. Polyphenylene sulfide resin composition, wherein the ratio X / Y of is greater than 1 and less than 7.
(Ca) Mohs hardness is more than 2 and less than 4 (Cb) Melting point or softening point is 380 ° C or more, or
[2] For 100 parts by weight of (A) polyphenylene sulfide resin, 100 to 250 parts by weight of (B) irregularly shaped cross-section glass fiber, and (C) non-fiber inorganic filler (however, hexagonal boron nitride and magnesium hydroxide). , Talk, magnesium oxide, and aluminum nitride) are blended in 25 to 150 parts by weight in a polyphenylene sulfide resin composition, wherein the blended weight X of the (B) modified cross-sectional glass fiber and the (C) non-fiber A polyphenylene sulfide resin composition, wherein the ratio X / Y to the compounding weight Y of the system-inorganic filler is greater than 1 and less than 7.
　本発明の成形品は、以下の構成を有する。すなわち、
上記ポリフェニレンサルファイド樹脂組成物からなる成形品、である。 The molded product of the present invention has the following constitution. That is,
A molded product made of the above-mentioned polyphenylene sulfide resin composition.
　本発明のポリフェニレンサルファイド樹脂組成物は、前記（Ｂ）異形断面ガラス繊維の長径（断面の最長の直線距離）と短径（長径と直角方向の最長の直線距離）の比が１．３～１０であることが好ましい。 In the polyphenylene sulfide resin composition of the present invention, the ratio of the major axis (the longest linear distance in the cross section) to the minor axis (the longest linear distance in the direction perpendicular to the major axis) of the (B) deformed cross-section glass fiber is 1.3 to 10. Is preferable.
　本発明のポリフェニレンサルファイド樹脂組成物は、前記（Ａ）ポリフェニレンサルファイド樹脂１００重量部に対する（Ｂ）異形断面ガラス繊維の配合重量Ｘと（Ｃ）非繊維系無機フィラーの配合重量Ｙの比率Ｘ／Ｙが１より大きく５未満であることが好ましい。 In the polyphenylene sulfide resin composition of the present invention, the ratio X / Y of the compounding weight X of (B) irregularly cross-sectional glass fiber to 100 parts by weight of the (A) polyphenylene sulfide resin and (C) compounding weight Y of non-fiber inorganic filler Is more than 1 and less than 5.
　本発明のポリフェニレンサルファイド樹脂組成物は、前記記載の（Ｃ）非繊維系無機フィラーが炭酸カルシウムであることが好ましい。 In the polyphenylene sulfide resin composition of the present invention, it is preferable that the (C) non-fiber-based inorganic filler described above is calcium carbonate.
　本発明の成形品は、成形品が筐体部品であることが好ましい。 In the molded product of the present invention, it is preferable that the molded product is a housing component.
　本発明は、機械物性、および寸法安定性に優れ、特に異方性が大幅に抑制され、湿熱処理時の膨張が抑制されたポリフェニレンサルファイド樹脂組成物とその成形品を提供することができる。 The present invention can provide a polyphenylene sulfide resin composition and a molded product thereof, which are excellent in mechanical properties and dimensional stability, particularly in which anisotropy is significantly suppressed and expansion during wet heat treatment is suppressed.
線膨張係数、膨潤性およびクリープ特性を評価する際に用いる試験片作成のための切削加工用平板４の形状を示す（a）平面図、および（ｂ）側面図である。It is (a) plan view and (b) side view which shows the shape of the plate 4 for cutting process for making a test piece used when evaluating a linear expansion coefficient, swellability and creep property. 線膨張係数測定時の試験片の切削位置を示す図である。It is a figure which shows the cutting position of the test piece at the time of measuring the coefficient of linear expansion. 線膨張係数を測定するための試験片の形状を示す（a）平面図、および（ｂ）側面図である。It is (a) plan view and (b) side view which shows the shape of the test piece for measuring a linear expansion coefficient.
　以下、本発明の実施の形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
　本発明で用いられる（Ａ）ＰＰＳ樹脂は、下記構造式で示される繰り返し単位を有する重合体であり、耐熱性の観点からは上記構造式で示される繰り返し単位を７０モル％以上、更には９０モル％以上含む重合体が好ましい。 The (A) PPS resin used in the present invention is a polymer having a repeating unit represented by the following structural formula, and from the viewpoint of heat resistance, the repeating unit represented by the above structural formula is 70 mol% or more, further 90. A polymer containing mol% or more is preferable.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　またＰＰＳ樹脂はその繰り返し単位の３０モル％未満程度が、下記の構造を有する繰り返し単位等で構成されていてもよい。 Further, less than 30 mol% of the repeating unit of the PPS resin may be composed of a repeating unit having the following structure or the like.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　以下に、本発明で用いるＰＰＳ樹脂の製造方法を述べる。まず、使用するポリハロゲン化芳香族化合物、スルフィド化剤、重合溶媒、分子量調節剤、重合助剤および重合安定剤の内容について説明する。 The method for producing the PPS resin used in the present invention will be described below. First, the contents of the polyhalogenated aromatic compound, the sulfide agent, the polymerization solvent, the molecular weight modifier, the polymerization aid and the polymerization stabilizer to be used will be described.
　［ポリハロゲン化芳香族化合物］
　ポリハロゲン化芳香族化合物とは、１分子中にハロゲン原子を２個以上有する化合物をいう。具体例としては、ｐ－ジクロロベンゼン、ｍ－ジクロロベンゼン、ｏ－ジクロロベンゼン、１，３，５－トリクロロベンゼン、１，２，４－トリクロロベンゼン、１，２，４，５－テトラクロロベンゼン、ヘキサクロロベンゼン、２，５－ジクロロトルエン、２，５－ジクロロ－ｐ－キシレン、１，４－ジブロモベンゼン、１，４－ジヨードベンゼン、１－メトキシ－２，５－ジクロロベンゼンなどのポリハロゲン化芳香族化合物が挙げられ、好ましくはｐ－ジクロロベンゼンが用いられる。また、異なる２種以上のポリハロゲン化芳香族化合物を組み合わせて共重合体とすることも可能であるが、ｐ－ジハロゲン化芳香族化合物を主要成分とすることが好ましい。 [Polyhalogenated aromatic compounds]
The polyhalogenated aromatic compound is a compound having two or more halogen atoms in one molecule. Specific examples include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, and hexa. Polyhalogenated fragrances such as chlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 1-methoxy-2,5-dichlorobenzene Group compounds are mentioned, and p-dichlorobenzene is preferably used. It is also possible to combine two or more different polyhalogenated aromatic compounds to form a copolymer, but it is preferable that the p-dihalogenated aromatic compound is the main component.
　ポリハロゲン化芳香族化合物の使用量は、加工に適した粘度のＰＰＳ樹脂を得る点から、スルフィド化剤１モル当たり０．９から２．０モル、好ましくは０．９５から１．５モル、更に好ましくは１．００５から１．２モルの範囲が例示できる。 The amount of the polyhalogenated aromatic compound used is 0.9 to 2.0 mol, preferably 0.95 to 1.5 mol, per mol of the sulfidizing agent, from the viewpoint of obtaining a PPS resin having a viscosity suitable for processing. More preferably, the range of 1.005 to 1.2 mol can be exemplified.
　［スルフィド化剤］
　スルフィド化剤としては、アルカリ金属硫化物、アルカリ金属水硫化物、および硫化水素が挙げられる。 [Sulfide agent]
Examples of the sulfidizing agent include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfides.
　アルカリ金属硫化物の具体例としては、例えば硫化リチウム、硫化ナトリウム、硫化カリウム、硫化ルビジウム、硫化セシウムおよびこれら２種以上の混合物を挙げることができ、なかでも硫化ナトリウムが好ましく用いられる。これらのアルカリ金属硫化物は、水和物または水性混合物として、あるいは無水物の形で用いることができる。 Specific examples of alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures of two or more of these, and sodium sulfide is preferably used. These alkali metal sulfides can be used as hydrates or aqueous mixtures, or in the form of anhydrides.
　アルカリ金属水硫化物の具体例としては、例えば水硫化ナトリウム、水硫化カリウム、水硫化リチウム、水硫化ルビジウム、水硫化セシウムおよびこれら２種以上の混合物を挙げることができ、なかでも水硫化ナトリウムが好ましく用いられる。これらのアルカリ金属水硫化物は、水和物または水性混合物として、あるいは無水物の形で用いることができる。 Specific examples of the alkali metal hydrosulfide include sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and a mixture of two or more of these, among which sodium hydrosulfide is used. It is preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures, or in the form of anhydrides.
　また、アルカリ金属水硫化物とアルカリ金属水酸化物から、反応系においてｉｎ　ｓｉｔｕで調製されるスルフィド化剤も用いることができる。また、アルカリ金属水硫化物とアルカリ金属水酸化物からスルフィド化剤を調整し、これを重合槽に移して用いることができる。 Further, a sulfidizing agent prepared in situ in the reaction system from alkali metal hydrosulfide and alkali metal hydroxide can also be used. Further, a sulfidizing agent can be prepared from alkali metal hydrosulfide and alkali metal hydroxide, and this can be transferred to a polymerization tank for use.
　あるいは、水酸化リチウム、水酸化ナトリウムなどのアルカリ金属水酸化物と硫化水素から反応系においてｉｎ　ｓｉｔｕで調製されるスルフィド化剤も用いることができる。また、水酸化リチウム、水酸化ナトリウムなどのアルカリ金属水酸化物と硫化水素からスルフィド化剤を調整し、これを重合槽に移して用いることができる。 Alternatively, a sulfidizing agent prepared in situ in the reaction system from alkali metal hydroxides such as lithium hydroxide and sodium hydroxide and hydrogen sulfide can also be used. Further, a sulfidizing agent can be prepared from alkali metal hydroxides such as lithium hydroxide and sodium hydroxide and hydrogen sulfide, and this can be transferred to a polymerization tank for use.
　仕込みスルフィド化剤の量は、脱水操作などにより重合反応開始前にスルフィド化剤の一部損失が生じる場合には、実際の仕込み量から当該損失分を差し引いた残存量を意味するものとする。 The amount of the charged sulfidating agent shall mean the residual amount obtained by subtracting the lost amount from the actual charged amount when a partial loss of the sulfidizing agent occurs before the start of the polymerization reaction due to a dehydration operation or the like.
　なお、スルフィド化剤と共に、アルカリ金属水酸化物および／またはアルカリ土類金属水酸化物を併用することも可能である。アルカリ金属水酸化物の具体例としては、例えば水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化ルビジウム、水酸化セシウムおよびこれら２種以上の混合物を好ましいものとして挙げることができ、アルカリ土類金属水酸化物の具体例としては、例えば水酸化カルシウム、水酸化ストロンチウム、水酸化バリウムなどが挙げられ、なかでも水酸化ナトリウムが好ましく用いられる。 It is also possible to use an alkali metal hydroxide and / or an alkaline earth metal hydroxide in combination with the sulfidizing agent. Specific examples of the alkali metal hydroxide include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide and a mixture of two or more of these, and alkaline earth. Specific examples of the metal hydroxide include calcium hydroxide, strontium hydroxide, barium hydroxide and the like, and sodium hydroxide is preferably used.
　スルフィド化剤として、アルカリ金属水硫化物を用いる場合には、アルカリ金属水酸化物を同時に使用することが特に好ましいが、この使用量はアルカリ金属水硫化物１モルに対し０．９５から１．２０モル、好ましくは１．００から１．１５モル、更に好ましくは１．００５から１．１００モルの範囲が例示できる。 When alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use alkali metal hydroxide at the same time, but the amount used is 0.95 to 1. per 1 mol of alkali metal hydrosulfide. An example is in the range of 20 mol, preferably 1.00 to 1.15 mol, more preferably 1.005 to 1.100 mol.
　［重合溶媒］
　重合溶媒としては有機極性溶媒を用いることが好ましい。具体例としては、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドンなどのＮ－アルキルピロリドン類、Ｎ－メチル－ε－カプロラクタムなどのカプロラクタム類、１，３－ジメチル－２－イミダゾリジノン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、ヘキサメチルリン酸トリアミド、ジメチルスルホン、テトラメチレンスルホキシドなどに代表されるアプロチック有機溶媒、およびこれらの混合物などが挙げられ、これらはいずれも反応の安定性が高いために好ましく使用される。これらのなかでも、特にＮ－メチル－２－ピロリドン（以下、ＮＭＰと略記することもある）が好ましく用いられる。 [Polymerization solvent]
It is preferable to use an organic polar solvent as the polymerization solvent. Specific examples include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, caprolactams such as N-methyl-ε-caprolactam, and 1,3-dimethyl-2-imidazolidi. Examples thereof include aprotic organic solvents typified by non-, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphate triamide, dimethylsulfone, tetramethylenesulfoxide, and mixtures thereof, all of which are used. It is preferably used because of its high reaction stability. Among these, N-methyl-2-pyrrolidone (hereinafter, may be abbreviated as NMP) is particularly preferably used.
　有機極性溶媒の使用量は、スルフィド化剤１モル当たり２．０モルから１０モル、好ましくは２．２５から６．０モル、より好ましくは２．５から５．５モルの範囲が選択される。 The amount of the organic polar solvent used is selected in the range of 2.0 to 10 mol, preferably 2.25 to 6.0 mol, more preferably 2.5 to 5.5 mol, per 1 mol of the sulfidizing agent. ..
　［分子量調節剤］
　生成するＰＰＳ樹脂の末端を形成させるか、あるいは重合反応や分子量を調節するなどのために、モノハロゲン化化合物（必ずしも芳香族化合物でなくともよい）を、上記ポリハロゲン化芳香族化合物と併用することができる。 [Molecular weight regulator]
A monohalogenated compound (not necessarily an aromatic compound) is used in combination with the polyhalogenated aromatic compound in order to form the terminal of the PPS resin to be produced, or to adjust the polymerization reaction or molecular weight. be able to.
　［重合助剤］
　比較的高重合度のＰＰＳ樹脂をより短時間で得るために重合助剤を用いることも好ましい態様の一つである。ここで重合助剤とは得られるＰＰＳ樹脂の粘度を増大させる作用を有する物質を意味する。このような重合助剤の具体例としては、例えば有機カルボン酸塩、水、アルカリ金属塩化物、有機スルホン酸塩、硫酸アルカリ金属塩、アルカリ土類金属酸化物、アルカリ金属リン酸塩およびアルカリ土類金属リン酸塩などが挙げられる。これらは単独であっても、また２種以上を同時に用いることもできる。なかでも、有機カルボン酸塩および／または水が好ましく用いられる。 [Polymerization aid]
It is also one of the preferable embodiments to use a polymerization aid in order to obtain a PPS resin having a relatively high degree of polymerization in a shorter time. Here, the polymerization aid means a substance having an action of increasing the viscosity of the obtained PPS resin. Specific examples of such polymerization aids include, for example, organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates and alkaline soils. Examples include metal phosphates. These can be used alone or in combination of two or more. Of these, organic carboxylates and / or water are preferably used.
　上記アルカリ金属カルボン酸塩とは、一般式Ｒ（ＣＯＯＭ）ｎ（式中、Ｒは、炭素数１～２０を有するアルキル基、シクロアルキル基、アリール基、アルキルアリール基またはアリールアルキル基である。Ｍは、リチウム、ナトリウム、カリウム、ルビジウムおよびセシウムから選ばれるアルカリ金属である。ｎは１の整数である。）で表される化合物である。アルカリ金属カルボン酸塩は、水和物、無水物または水溶液としても用いることができる。アルカリ金属カルボン酸塩の具体例としては、例えば、酢酸リチウム、酢酸ナトリウム、酢酸カリウム、プロピオン酸ナトリウム、吉草酸リチウム、安息香酸ナトリウム、フェニル酢酸ナトリウム、ｐ－トルイル酸カリウム、およびそれらの混合物などを挙げることができる。 The alkali metal carboxylate is a general formula R (COMM) n (in the formula, R is an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group having 1 to 20 carbon atoms. M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium. N is an integer of 1). Alkali metal carboxylates can also be used as hydrates, anhydrides or aqueous solutions. Specific examples of the alkali metal carboxylate include lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluic acid, and mixtures thereof. Can be mentioned.
　アルカリ金属カルボン酸塩は、有機酸と、水酸化アルカリ金属、炭酸アルカリ金属塩および重炭酸アルカリ金属塩よりなる群から選ばれる一種以上の化合物とを、ほぼ等化学当量ずつ添加して反応させることにより形成させてもよい。上記アルカリ金属カルボン酸塩の中で、リチウム塩は反応系への溶解性が高く助剤効果が大きいが高価であり、カリウム、ルビジウムおよびセシウム塩は反応系への溶解性が不十分であると思われるため、安価で、重合系への適度な溶解性を有する酢酸ナトリウムが最も好ましく用いられる。 The alkali metal carboxylate is a reaction in which an organic acid and one or more compounds selected from the group consisting of alkali metal hydroxide, alkali metal carbonate and alkali metal bicarbonate are added in approximately equal chemical equivalents and reacted. It may be formed by. Among the above alkali metal carboxylates, the lithium salt has high solubility in the reaction system and has a large auxiliary effect, but is expensive, and the potassium, rubidium and cesium salts have insufficient solubility in the reaction system. Therefore, sodium acetate, which is inexpensive and has an appropriate solubility in a polymerization system, is most preferably used.
　これら重合助剤を用いる場合の使用量は、仕込みアルカリ金属硫化物１モルに対し、通常０．０１モル～０．７モルの範囲であり、より高い重合度を得る意味においては０．１～０．６モルの範囲が好ましく、０．２～０．５モルの範囲がより好ましい。 When these polymerization aids are used, the amount used is usually in the range of 0.01 mol to 0.7 mol with respect to 1 mol of the charged alkali metal sulfide, and is 0.1 to 0.1 in the sense of obtaining a higher degree of polymerization. The range of 0.6 mol is preferable, and the range of 0.2 to 0.5 mol is more preferable.
　また水を重合助剤として用いることは、流動性と高靭性が高度にバランスした樹脂組成物を得る上で有効な手段の一つである。その場合の添加量は、仕込みアルカリ金属硫化物１モルに対し、通常０．５モル～１５モルの範囲であり、より高い重合度を得る意味においては０．６～１０モルの範囲が好ましく、１～５モルの範囲がより好ましい。 Also, using water as a polymerization aid is one of the effective means for obtaining a resin composition in which fluidity and high toughness are highly balanced. In that case, the amount to be added is usually in the range of 0.5 mol to 15 mol with respect to 1 mol of the charged alkali metal sulfide, and is preferably in the range of 0.6 to 10 mol in order to obtain a higher degree of polymerization. The range of 1 to 5 mol is more preferable.
　これら重合助剤の添加時期には特に指定はなく、後述する前工程時、重合開始時、重合途中のいずれの時点で添加してもよく、また複数回に分けて添加してもよいが、重合助剤としてアルカリ金属カルボン酸塩を用いる場合は前工程開始時或いは重合開始時に同時に添加することが、添加が容易である点からより好ましい。また水を重合助剤として用いる場合は、ポリハロゲン化芳香族化合物を仕込んだ後、重合反応途中で添加することが効果的である。 The timing of addition of these polymerization aids is not particularly specified, and may be added at any time of the pre-process, the start of polymerization, and the middle of polymerization, which will be described later, or may be added in a plurality of times. When an alkali metal carboxylate is used as the polymerization aid, it is more preferable to add it at the same time as the start of the previous step or the start of polymerization because it is easy to add. When water is used as a polymerization aid, it is effective to add the polyhalogenated aromatic compound in the middle of the polymerization reaction after charging it.
　［重合安定剤］
　重合反応系を安定化し、副反応を防止するために、重合安定剤を用いることもできる。重合安定剤は、重合反応系の安定化に寄与し、望ましくない副反応を抑制する。副反応の一つの目安としては、チオフェノールの生成が挙げられ、重合安定剤の添加によりチオフェノールの生成を抑えることができる。重合安定剤の具体例としては、アルカリ金属水酸化物、アルカリ金属炭酸塩、アルカリ土類金属水酸化物、およびアルカリ土類金属炭酸塩などの化合物が挙げられる。そのなかでも、水酸化ナトリウム、水酸化カリウム、および水酸化リチウムなどのアルカリ金属水酸化物が好ましい。上述のアルカリ金属カルボン酸塩も重合安定剤として作用するので、本発明で使用する重合安定剤の一つに入る。また、スルフィド化剤としてアルカリ金属水硫化物を用いる場合には、アルカリ金属水酸化物を同時に使用することが特に好ましいことを前述したが、ここでスルフィド化剤に対して過剰となるアルカリ金属水酸化物も重合安定剤となり得る。 [Polymerization stabilizer]
A polymerization stabilizer can also be used to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to the stabilization of the polymerization reaction system and suppresses unwanted side reactions. One guideline for the side reaction is the production of thiophenol, and the production of thiophenol can be suppressed by adding a polymerization stabilizer. Specific examples of the polymerization stabilizer include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, and alkaline earth metal carbonates. Among them, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferable. Since the above-mentioned alkali metal carboxylate also acts as a polymerization stabilizer, it is one of the polymerization stabilizers used in the present invention. Further, when an alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use the alkali metal hydroxide at the same time, but here, the alkali metal water which is excessive with respect to the sulfidizing agent. Oxides can also be polymerization stabilizers.
　これら重合安定剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができる。重合安定剤は、仕込みアルカリ金属硫化物１モルに対して、通常０．０２～０．２モル、好ましくは０．０３～０．１モル、より好ましくは０．０４～０．０９モルの割合で使用することが好ましい。この好ましい割合であると安定化効果が十分であり、一方、ポリマー収率に優れる。 These polymerization stabilizers can be used alone or in combination of two or more. The ratio of the polymerization stabilizer to 1 mol of the charged alkali metal sulfide is usually 0.02 to 0.2 mol, preferably 0.03 to 0.1 mol, and more preferably 0.04 to 0.09 mol. It is preferable to use in. At this preferable ratio, the stabilizing effect is sufficient, while the polymer yield is excellent.
　重合安定剤の添加時期には特に指定はなく、後述する前工程時、重合開始時、重合途中のいずれの時点で添加してもよく、また複数回に分けて添加してもよいが、前工程開始時或いは重合開始時に同時に添加することがより好ましい。 The timing of addition of the polymerization stabilizer is not particularly specified, and it may be added at any time of the pre-process, the start of polymerization, and the middle of polymerization, which will be described later, or it may be added in a plurality of times. It is more preferable to add at the same time at the start of the process or the start of polymerization.
　次に、前工程、重合反応工程、回収工程を、順を追って具体的に説明する。 Next, the pre-process, the polymerization reaction process, and the recovery process will be specifically described step by step.
　［前工程］
　スルフィド化剤は通常水和物の形で使用されるが、ポリハロゲン化芳香族化合物を添加する前に、有機極性溶媒とスルフィド化剤を含む混合物を昇温し、過剰量の水を系外に除去することが好ましい。なお、この操作により水を除去し過ぎた場合には、不足分の水を添加して補充することが好ましい。 [pre-process]
The sulfidizing agent is usually used in the form of a hydrate, but before adding the polyhalogenated aromatic compound, the mixture containing the organic polar solvent and the sulfidizing agent is heated to remove an excess amount of water. It is preferable to remove it. If too much water is removed by this operation, it is preferable to add the insufficient water to replenish the water.
　また、上述したように、スルフィド化剤として、アルカリ金属水硫化物とアルカリ金属水酸化物から、反応系においてｉｎ　ｓｉｔｕで、あるいは重合槽とは別の槽で調製されるアルカリ金属硫化物も用いることができる。この方法には特に制限はないが、好ましくは不活性ガス雰囲気下、常温～１５０℃、好ましくは常温から１００℃の温度範囲で、有機極性溶媒にアルカリ金属水硫化物とアルカリ金属水酸化物を加え、常圧または減圧下、少なくとも１５０℃以上、好ましくは１８０～２４５℃まで昇温し、水分を留去させる方法が挙げられる。この段階で重合助剤を加えてもよい。また、水分の留去を促進するために、トルエンなどを加えて反応を行ってもよい。 Further, as described above, as the sulfidizing agent, an alkali metal sulfide prepared from alkali metal hydrosulfide and alkali metal hydroxide in situ in the reaction system or in a tank separate from the polymerization tank is also used. be able to. This method is not particularly limited, but preferably in an inert gas atmosphere, in a temperature range of room temperature to 150 ° C., preferably room temperature to 100 ° C., alkali metal hydrosulfide and alkali metal hydroxide are used as organic polar solvents. In addition, there is a method in which the temperature is raised to at least 150 ° C. or higher, preferably 180 to 245 ° C. under normal pressure or reduced pressure to distill off water. A polymerization aid may be added at this stage. Further, in order to promote the distillation of water, toluene or the like may be added to carry out the reaction.
　重合反応における、重合系内の水分量は、仕込みスルフィド化剤１モル当たり０．５～１０．０モルであることが好ましい。ここで重合系内の水分量とは重合系に仕込まれた水分量から重合系外に除去された水分量を差し引いた量である。また、仕込まれる水は、水、水溶液、結晶水などのいずれの形態であってもよい。 The amount of water in the polymerization system in the polymerization reaction is preferably 0.5 to 10.0 mol per mol of the charged sulfidizing agent. Here, the amount of water in the polymerization system is the amount obtained by subtracting the amount of water removed from the polymerization system from the amount of water charged in the polymerization system. Further, the water to be charged may be in any form such as water, an aqueous solution, and water of crystallization.
　［重合反応工程］
　有機極性溶媒中でスルフィド化剤とポリハロゲン化芳香族化合物とを２００℃以上２９０℃未満の温度範囲内で反応させることによりＰＰＳ樹脂粉粒体を製造することが好ましい。 [Polymerization reaction step]
It is preferable to produce PPS resin powder or granular material by reacting a sulfidizing agent and a polyhalogenated aromatic compound in an organic polar solvent within a temperature range of 200 ° C. or higher and lower than 290 ° C.
　重合反応工程を開始するに際しては、好ましくは不活性ガス雰囲気下、常温～２１５℃、好ましくは１００～２１５℃の温度範囲で、有機極性溶媒にスルフィド化剤とポリハロゲン化芳香族化合物を加える。この段階で重合助剤を加えてもよい。これらの原料の仕込み順序は、順不同であってもよく、同時であってもさしつかえない。 When starting the polymerization reaction step, a sulfidizing agent and a polyhalogenated aromatic compound are added to the organic polar solvent in a temperature range of preferably normal temperature to 215 ° C., preferably 100 to 215 ° C. in an inert gas atmosphere. A polymerization aid may be added at this stage. The order in which these raw materials are charged may be random or simultaneous.
　かかる混合物を通常２００℃～２９０℃の範囲に昇温する。昇温速度に特に制限はないが、通常０．０１～５℃／分の速度が選択され、０．１～３℃／分の範囲がより好ましい。 The temperature of such a mixture is usually raised to the range of 200 ° C to 290 ° C. The rate of temperature rise is not particularly limited, but usually a rate of 0.01 to 5 ° C./min is selected, and a range of 0.1 to 3 ° C./min is more preferable.
　一般に、最終的には２５０～２９０℃の温度まで昇温し、その温度で通常０．２５～５０時間、好ましくは０．５～２０時間反応させる。 In general, the temperature is finally raised to a temperature of 250 to 290 ° C., and the reaction is carried out at that temperature for usually 0.25 to 50 hours, preferably 0.5 to 20 hours.
　最終温度に到達させる前の段階で、例えば２００℃～２４５℃で一定時間反応させた後、２７０～２９０℃に昇温する方法は、より高い重合度を得る上で有効である。この際、２００℃～２４５℃での反応時間としては、通常０．２５～２０時間の範囲が選択され、好ましくは０．２５～１０時間の範囲が選択される。 A method of reacting at 200 ° C. to 245 ° C. for a certain period of time and then raising the temperature to 270 to 290 ° C. before reaching the final temperature is effective in obtaining a higher degree of polymerization. At this time, the reaction time at 200 ° C. to 245 ° C. is usually selected in the range of 0.25 to 20 hours, preferably in the range of 0.25 to 10 hours.
　なお、より高重合度のポリマーを得るためには、複数段階で重合を行うことが有効である。複数段階で重合を行う際は、２４５℃における系内のポリハロゲン化芳香族化合物の転化率が、４０モル％以上、好ましくは６０モル％に達した時点であることが有効である。 In order to obtain a polymer with a higher degree of polymerization, it is effective to carry out polymerization in a plurality of steps. When the polymerization is carried out in a plurality of steps, it is effective that the conversion rate of the polyhalogenated aromatic compound in the system at 245 ° C. reaches 40 mol% or more, preferably 60 mol%.
　［回収工程］
　重合終了後に、重合体、溶媒などを含む重合反応物から固形物を回収する。 [Recovery process]
After completion of the polymerization, a solid substance is recovered from the polymerization reaction product containing a polymer, a solvent and the like.
　ＰＰＳ樹脂の最も好ましい回収方法は、急冷条件下に行うことであり、この回収方法の好ましい一つの方法としてフラッシュ法が挙げられる。フラッシュ法とは、重合反応物を高温高圧（通常２５０℃以上、８ｋｇ／ｃｍ２以上）の状態から常圧もしくは減圧の雰囲気中へフラッシュさせ、溶媒回収と同時に重合体を粉粒体状にして回収する方法であり、ここでいうフラッシュとは、重合反応物をノズルから噴出させることを意味する。フラッシュさせる雰囲気は、具体的には例えば常圧中の窒素または水蒸気が挙げられ、その温度は通常１５０℃～２５０℃の範囲が選択される。 The most preferable recovery method of the PPS resin is to carry out under quenching conditions, and one preferred method of this recovery method is the flash method. In the flash method, the polymerization reaction product is flushed from a high temperature and high pressure (usually 250 ° C. or higher, 8 kg / cm 2 or higher) into an atmosphere of normal pressure or reduced pressure, and the polymer is made into powder or granular material at the same time as the solvent is recovered. This is a recovery method, and the term “flash” as used herein means that the polymerization reaction product is ejected from the nozzle. Specific examples of the flashing atmosphere include nitrogen or water vapor under normal pressure, and the temperature is usually selected in the range of 150 ° C. to 250 ° C.
　フラッシュ法は、溶媒回収と同時に固形物を回収することができ、また回収時間も比較的短くできることから、経済性に優れた回収方法である。この回収方法では、固化過程でＮａに代表されるイオン性化合物や有機系低重合度物（オリゴマー）がポリマー中に取り込まれやすい傾向がある。 The flash method is an economical recovery method because the solid matter can be recovered at the same time as the solvent is recovered and the recovery time can be relatively short. In this recovery method, ionic compounds typified by Na and organic low-degree-of-polymerization products (oligomers) tend to be easily incorporated into the polymer during the solidification process.
　但し、本発明に用いられるＰＰＳ樹脂の回収法は、フラッシュ法に限定されるものではない。本発明の要件を満たす方法であれば、徐冷して粒子状のポリマーを回収する方法（クエンチ法）を用いても構わない。しかし、経済性、性能を鑑みた場合、本発明の製造方法はフラッシュ法で回収されたＰＰＳ樹脂を用いることがより好ましい。 However, the method for recovering the PPS resin used in the present invention is not limited to the flash method. As long as the method satisfies the requirements of the present invention, a method of slowly cooling to recover the particulate polymer (quenching method) may be used. However, from the viewpoint of economy and performance, it is more preferable to use the PPS resin recovered by the flash method in the production method of the present invention.
　本発明では、ＰＰＳ樹脂として、たとえば上記重合反応工程、回収工程を経た後、熱酸化処理を行ったものを用いることが好ましい。好ましくは、熱酸化処理工程の前に熱水処理、酸処理を含むことが好ましい。また、酸処理する工程や熱水処理する工程の前に有機溶媒により洗浄する工程を含んでもよい。 In the present invention, it is preferable to use a PPS resin that has undergone the above-mentioned polymerization reaction step and recovery step and then undergoes thermal oxidation treatment. It is preferable to include hot water treatment and acid treatment before the thermal oxidation treatment step. Further, a step of washing with an organic solvent may be included before the step of acid treatment or the step of hot water treatment.
　本発明における酸処理に用いる酸は、ＰＰＳ樹脂を分解する作用を有しないものであれば特に制限はなく、酢酸、塩酸、硫酸、リン酸、珪酸、炭酸およびプロピル酸などが挙げられ、なかでも酢酸および塩酸がより好ましく用いられるが、硝酸のようなＰＰＳ樹脂を分解、劣化させるものは好ましくない。 The acid used for the acid treatment in the present invention is not particularly limited as long as it does not have an action of decomposing the PPS resin, and examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid. Acetic acid and hydrochloric acid are more preferably used, but those that decompose and deteriorate PPS resins such as nitric acid are not preferable.
　酸の水溶液を用いるときの水は、蒸留水あるいは脱イオン水であることが好ましい。酸の水溶液は、ｐＨ１～７が好ましく、ｐＨ２～４がより好ましい。ｐＨが７以下であるとＰＰＳ樹脂の金属含有量が増大せず、ｐＨが１以上であるとＰＰＳ樹脂の揮発成分が多くならない。 When using an aqueous acid solution, the water is preferably distilled water or deionized water. The aqueous acid solution preferably has a pH of 1 to 7, more preferably pH 2 to 4. When the pH is 7 or less, the metal content of the PPS resin does not increase, and when the pH is 1 or more, the volatile components of the PPS resin do not increase.
　酸処理の方法は、酸または酸の水溶液にＰＰＳ樹脂を浸漬せしめることが好ましく、必要により適宜撹拌および加熱することも可能である。加熱する際の温度は８０～２５０℃が好ましく、１２０～２００℃がより好ましく、１５０～２００℃がさらに好ましい。加熱する際の温度が８０℃以上であると酸処理効果が十分で、金属含有量が増大せず、２５０℃以下であると圧力が高くなりすぎることがないため安全上好ましい。また、酸の水溶液でＰＰＳ樹脂を浸漬せしめて処理する際のｐＨは、酸処理により８以下となることが好ましく、ｐＨ２～８がより好ましい。ｐＨが８以下であると得られるＰＰＳ樹脂の金属含有量が増大しない。 As a method of acid treatment, it is preferable to immerse the PPS resin in an acid or an aqueous solution of an acid, and it is also possible to appropriately stir and heat if necessary. The temperature at the time of heating is preferably 80 to 250 ° C, more preferably 120 to 200 ° C, and even more preferably 150 to 200 ° C. When the temperature at the time of heating is 80 ° C. or higher, the acid treatment effect is sufficient, the metal content does not increase, and when the temperature is 250 ° C. or lower, the pressure does not become too high, which is preferable for safety. Further, the pH when the PPS resin is immersed in an aqueous acid solution for treatment is preferably 8 or less by the acid treatment, and more preferably pH 2 to 8. When the pH is 8 or less, the metal content of the obtained PPS resin does not increase.
　酸処理の時間は、ＰＰＳ樹脂と酸の反応が十分に平衡となる時間が好ましく、８０℃で処理する場合は２～２４時間が好ましく、２００℃で処理する場合は０．０１～５時間が好ましい。 The acid treatment time is preferably a time during which the reaction between the PPS resin and the acid is sufficiently equilibrated, preferably 2 to 24 hours when treated at 80 ° C., and 0.01 to 5 hours when treated at 200 ° C. preferable.
　酸処理におけるＰＰＳ樹脂と酸または酸の水溶液との割合は、ＰＰＳ樹脂が酸または酸の水溶液中に十分に浸漬された状態で処理することが好ましく、ＰＰＳ樹脂５００ｇに対して、酸または酸の水溶液０．５～５００Ｌが好ましく、１～１００Ｌがより好ましく、２．５～２０Ｌがさらに好ましい。ＰＰＳ樹脂５００ｇに対して酸または酸の水溶液が０．５Ｌ以上であるとＰＰＳ樹脂が水溶液に十分浸漬するため洗浄が十分で、ＰＰＳ樹脂の金属含有量が増大しない。また、ＰＰＳ樹脂５００ｇに対して、酸または酸の水溶液が５００Ｌ以下であると、ＰＰＳ樹脂に対する溶液量が適切で生産効率が良好である。 The ratio of the PPS resin to the acid or the aqueous solution of the acid in the acid treatment is preferably treated in a state where the PPS resin is sufficiently immersed in the acid or the aqueous solution of the acid, and 500 g of the PPS resin is treated with the acid or the acid. The aqueous solution is preferably 0.5 to 500 L, more preferably 1 to 100 L, and even more preferably 2.5 to 20 L. When the acid or the aqueous solution of the acid is 0.5 L or more with respect to 500 g of the PPS resin, the PPS resin is sufficiently immersed in the aqueous solution, so that the washing is sufficient and the metal content of the PPS resin does not increase. Further, when the acid or the aqueous solution of the acid is 500 L or less with respect to 500 g of the PPS resin, the amount of the solution to the PPS resin is appropriate and the production efficiency is good.
　これらの酸処理は所定量の水および酸に所定量のＰＰＳ樹脂を投入し、圧力容器内で加熱・撹拌する方法、連続的に酸処理を施す方法などにより行われる。酸処理後の処理溶液から水溶液とＰＰＳ樹脂を分離する方法はふるいやフィルターを用いた濾過が簡便であり、自然濾過、加圧濾過、減圧濾過、遠心濾過などの方法が例示できる。処理液から分離されたＰＰＳ樹脂表面に残留している酸や不純物を除去するため、水または温水で数回洗浄することが好ましい。洗浄方法は濾過装置上のＰＰＳ樹脂に水をかけながら濾過する方法や、予め用意した水に、分離したＰＰＳ樹脂を投入した後に再度濾過するなどの方法で水溶液とＰＰＳ樹脂を分離する方法が例示できる。洗浄に用いる水は、蒸留水あるいは脱イオン水であることが好ましい。 These acid treatments are performed by adding a predetermined amount of PPS resin to a predetermined amount of water and acid, heating and stirring in a pressure vessel, and continuously performing acid treatment. As a method for separating the aqueous solution and the PPS resin from the treated solution after the acid treatment, filtration using a sieve or a filter is convenient, and methods such as natural filtration, pressure filtration, vacuum filtration, and centrifugal filtration can be exemplified. In order to remove acids and impurities remaining on the surface of the PPS resin separated from the treatment liquid, it is preferable to wash with water or warm water several times. Examples of the cleaning method include a method of filtering the PPS resin on the filtration device while sprinkling water on it, and a method of separating the aqueous solution and the PPS resin by adding the separated PPS resin to the water prepared in advance and then filtering again. it can. The water used for washing is preferably distilled water or deionized water.
　本発明では酸処理する工程の前に熱水処理を行うことが好ましく、その方法は次のとおりである。本発明における熱水処理に用いる水は、蒸留水あるいは脱イオン水であることが好ましい。熱水処理温度は８０～２５０℃が好ましく、１２０～２００℃がより好ましく、１５０～２００℃がさらに好ましい。熱水処理温度が８０℃以上であると熱水処理効果が十分で、揮発するガス発生量が少なく、２５０℃以下であると圧力が高くなりすぎることがないため安全上好ましい。 In the present invention, it is preferable to perform hot water treatment before the acid treatment step, and the method is as follows. The water used for the hot water treatment in the present invention is preferably distilled water or deionized water. The hot water treatment temperature is preferably 80 to 250 ° C., more preferably 120 to 200 ° C., and even more preferably 150 to 200 ° C. When the hot water treatment temperature is 80 ° C. or higher, the hot water treatment effect is sufficient, the amount of volatile gas generated is small, and when the hot water treatment temperature is 250 ° C. or lower, the pressure does not become too high, which is preferable for safety.
　熱水処理の時間は、ＰＰＳ樹脂と熱水による抽出処理が十分である時間が好ましく、８０℃で処理する場合は２～２４時間が好ましく、２００℃で処理する場合は０．０１～５時間が好ましい。 The hot water treatment time is preferably a time when the extraction treatment with PPS resin and hot water is sufficient, preferably 2 to 24 hours when the treatment is performed at 80 ° C., and 0.01 to 5 hours when the treatment is performed at 200 ° C. Is preferable.
　熱水処理におけるＰＰＳ樹脂と水との割合は、ＰＰＳ樹脂が水に十分に浸漬された状態で処理することが好ましく、ＰＰＳ樹脂５００ｇに対して、水０．５～５００Ｌが好ましく、１～１００Ｌがより好ましく、２．５～２０Ｌがさらに好ましい。ＰＰＳ樹脂５００ｇに対して水が０．５Ｌ以上であるとＰＰＳ樹脂が水に十分浸漬するため洗浄が十分で、揮発するガス発生量が増大しない。また、ＰＰＳ樹脂５００ｇに対して、水が５００Ｌ以下であると、ＰＰＳ樹脂に対する水の割合が適切で生産効率が良好である。 The ratio of PPS resin to water in the hot water treatment is preferably treated in a state where the PPS resin is sufficiently immersed in water, preferably 0.5 to 500 L of water with respect to 500 g of PPS resin, and 1 to 100 L. Is more preferable, and 2.5 to 20 L is further preferable. If the amount of water is 0.5 L or more with respect to 500 g of the PPS resin, the PPS resin is sufficiently immersed in the water, so that the cleaning is sufficient and the amount of volatile gas generated does not increase. Further, when the amount of water is 500 L or less with respect to 500 g of the PPS resin, the ratio of water to the PPS resin is appropriate and the production efficiency is good.
　これらの熱水処理の操作に特に制限は無く、所定量の水に所定量のＰＰＳ樹脂を投入し、圧力容器内で加熱・撹拌する方法、連続的に熱水処理を施す方法などにより行われる。熱水処理後の処理溶液から水溶液とＰＰＳ樹脂を分離する方法に特に制限は無いが、ふるいやフィルターを用いた濾過が簡便であり、自然濾過、加圧濾過、減圧濾過、遠心濾過などの方法が例示できる。処理液から分離されたＰＰＳ樹脂表面に残留している不純物を除去するため、水または温水で数回洗浄することが好ましい。洗浄方法に特に制限は無いが、濾過装置上のＰＰＳ樹脂に水をかけながら濾過する方法や、予め用意した水に、分離したＰＰＳ樹脂を投入した後に再度濾過するなどの方法で水溶液とＰＰＳ樹脂を分離する方法が例示できる。洗浄に用いる水は、蒸留水あるいは脱イオン水であることが好ましい。 The operation of these hot water treatments is not particularly limited, and is carried out by a method of adding a predetermined amount of PPS resin to a predetermined amount of water, heating and stirring in a pressure vessel, a method of continuously performing hot water treatment, and the like. .. There is no particular limitation on the method of separating the aqueous solution and the PPS resin from the treated solution after hot water treatment, but filtration using a sieve or a filter is convenient, and methods such as natural filtration, pressure filtration, vacuum filtration, and centrifugal filtration are available. Can be exemplified. In order to remove impurities remaining on the surface of the PPS resin separated from the treatment liquid, it is preferable to wash with water or warm water several times. The cleaning method is not particularly limited, but the aqueous solution and the PPS resin can be filtered by sprinkling water on the PPS resin on the filtration device, or by adding the separated PPS resin to the water prepared in advance and then filtering again. The method of separating the above can be exemplified. The water used for washing is preferably distilled water or deionized water.
　また、これら酸処理や熱水処理時のＰＰＳ末端基の分解を防ぐ観点から、酸処理や熱水処理を不活性雰囲気下とすることが好ましい。不活性雰囲気としては、窒素、ヘリウム、アルゴンなどがあげられるが、経済性の観点から窒素雰囲気下が好ましい。 Further, from the viewpoint of preventing the decomposition of PPS terminal groups during these acid treatments and hot water treatments, it is preferable that the acid treatments and hot water treatments are carried out in an inert atmosphere. Examples of the inert atmosphere include nitrogen, helium, and argon, but a nitrogen atmosphere is preferable from the viewpoint of economy.
　本発明では酸処理する工程や熱水処理する工程の前に有機溶媒により洗浄する工程を含んでもよく、その方法は次のとおりである。本発明でＰＰＳ樹脂の洗浄に用いる有機溶媒は、ＰＰＳ樹脂を分解する作用などを有しないものであれば特に制限はなく、例えばＮ－メチル－２－ピロリドン、ジメチルホルムアミド、ジメチルアセトアミド、１，３－ジメチルイミダゾリジノン、ヘキサメチルホスホラスアミド、ピペラジノン類などの含窒素極性溶媒、ジメチルスルホキシド、ジメチルスルホン、スルホランなどのスルホキシド・スルホン系溶媒、アセトン、メチルエチルケトン、ジエチルケトン、アセトフェノンなどのケトン系溶媒、ジメチルエーテル、ジプロピルエーテル、ジオキサン、テトラヒドロフランなどのエーテル系溶媒、クロロホルム、塩化メチレン、トリクロロエチレン、２塩化エチレン、パークロルエチレン、モノクロルエタン、ジクロルエタン、テトラクロルエタン、パークロルエタン、クロルベンゼンなどのハロゲン系溶媒、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、エチレングリコール、プロピレングリコール、フェノール、クレゾール、ポリエチレングリコール、ポリプロピレングリコールなどのアルコール・フェノール系溶媒およびベンゼン、トルエン、キシレンなどの芳香族炭化水素系溶媒などが挙げられる。これらの有機溶媒のうちでも、Ｎ－メチル－２－ピロリドン、アセトン、ジメチルホルムアミドおよびクロロホルムなどの使用が特に好ましい。また、これらの有機溶媒は、１種類または２種類以上の混合で使用される。 The present invention may include a step of washing with an organic solvent before the step of acid treatment or the step of hot water treatment, and the method is as follows. The organic solvent used for cleaning the PPS resin in the present invention is not particularly limited as long as it does not have an action of decomposing the PPS resin. For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, 1,3 -Nitrogen-containing polar solvents such as dimethylimidazolidinone, hexamethylphosphorasamide and piperazinones, sulfoxide-sulfone solvents such as dimethylsulfoxide, dimethylsulfone and sulfolane, ketone solvents such as acetone, methylethylketone, diethylketone and acetophenone, Ether-based solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, halogen-based solvents such as chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrachloroethane, perchlorethane, and chlorobenzene. , Methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol and other alcohol / phenol solvents and benzene, toluene, xylene and other aromatic hydrocarbon solvents. Can be mentioned. Among these organic solvents, the use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferable. Moreover, these organic solvents are used in one kind or a mixture of two or more kinds.
　有機溶媒による洗浄の方法としては、有機溶媒中にＰＰＳ樹脂を浸漬せしめるなどの方法があり、必要により適宜撹拌または加熱することも可能である。有機溶媒でＰＰＳ樹脂を洗浄する際の洗浄温度については特に制限はなく、常温～３００℃程度の任意の温度が選択できる。洗浄温度が高くなる程洗浄効率が高くなる傾向があるが、通常は常温～１５０℃の洗浄温度で十分効果が得られる。圧力容器中で、有機溶媒の沸点以上の温度で加圧下に洗浄することも可能である。また、洗浄時間についても特に制限はない。洗浄条件にもよるが、バッチ式洗浄の場合、通常５分間以上洗浄することにより十分な効果が得られる。また連続式で洗浄することも可能である。 As a method of cleaning with an organic solvent, there is a method such as immersing the PPS resin in the organic solvent, and it is also possible to appropriately stir or heat if necessary. The cleaning temperature when cleaning the PPS resin with an organic solvent is not particularly limited, and any temperature of about room temperature to 300 ° C. can be selected. The higher the cleaning temperature, the higher the cleaning efficiency tends to be, but usually, a sufficient effect can be obtained at a cleaning temperature of room temperature to 150 ° C. It is also possible to wash under pressure in a pressure vessel at a temperature higher than the boiling point of the organic solvent. In addition, there is no particular limitation on the cleaning time. Although it depends on the cleaning conditions, in the case of batch-type cleaning, a sufficient effect is usually obtained by cleaning for 5 minutes or more. It is also possible to wash continuously.
　これら酸処理、熱水処理または有機溶媒による洗浄は、これらを適宜組み合わせて行うことも可能である。 These acid treatment, hot water treatment, or cleaning with an organic solvent can be performed by combining these as appropriate.
　［加熱処理工程］
　本発明で用いられるＰＰＳ樹脂は、好ましくは上記酸処理、熱水処理または有機溶媒による洗浄をした後に、熱酸化処理を行ったものが好ましい。このように熱酸化処理を施すことにより、溶融成形加工時のガス発生量が減少すると共に、機械強度が向上しやすくなる。 [Heat treatment process]
The PPS resin used in the present invention is preferably one obtained by undergoing thermal oxidation treatment after the above acid treatment, hot water treatment or washing with an organic solvent. By performing the thermal oxidation treatment in this way, the amount of gas generated during the melt molding process is reduced, and the mechanical strength is likely to be improved.
　なお、ここで言う熱酸化処理とは、ＰＰＳ樹脂を、酸素雰囲気下においての加熱またはＨ２Ｏ２等の過酸化物もしくはＳ等の加硫剤を添加しての加熱による処理を施すことであるが、処理の簡便さから酸素雰囲気においての加熱が特に好ましい。 The thermal oxidation treatment referred to here is a treatment by heating the PPS resin in an oxygen atmosphere or by adding a peroxide such as H 2 O 2 or a vulcanizing agent such as S. However, heating in an oxygen atmosphere is particularly preferable because of the ease of treatment.
　ＰＰＳ樹脂の熱酸化処理のための加熱装置は、通常の熱風乾燥機でもよいし、回転式あるいは撹拌翼付の加熱装置であってもよいが、効率よく、しかもより均一に処理する場合は、回転式あるいは撹拌翼付の加熱装置を用いるのがより好ましい。熱酸化処理の際の雰囲気における酸素濃度は１体積％以上、更には２体積％以上とすることが望ましい。本発明の効果を発揮するためには、酸素濃度の上限は５体積％以下が好ましい。酸素濃度５体積％以下で熱酸化処理を行うことで、熱酸化処理が過剰に進行することがなく、熱酸化処理をおこなったＰＰＳ樹脂を含む成形品の靭性が損なわれることがない。一方、酸素濃度１体積％以上での熱酸化処理を行うことで、十分な熱酸化処理を行うことができ、揮発成分が少ないＰＰＳ樹脂を得ることができるので好ましい。 The heating device for the thermal oxidation treatment of the PPS resin may be a normal hot air dryer, a rotary type or a heating device with a stirring blade, but in the case of efficient and more uniform treatment, It is more preferable to use a heating device of a rotary type or a stirring blade. It is desirable that the oxygen concentration in the atmosphere during the thermal oxidation treatment is 1% by volume or more, more preferably 2% by volume or more. In order to exert the effect of the present invention, the upper limit of the oxygen concentration is preferably 5% by volume or less. By performing the thermal oxidation treatment at an oxygen concentration of 5% by volume or less, the thermal oxidation treatment does not proceed excessively, and the toughness of the molded product containing the PPS resin subjected to the thermal oxidation treatment is not impaired. On the other hand, it is preferable to perform the thermal oxidation treatment at an oxygen concentration of 1% by volume or more because a sufficient thermal oxidation treatment can be performed and a PPS resin having a small amount of volatile components can be obtained.
　ＰＰＳ樹脂の熱酸化処理温度は、１６０～２７０℃が好ましく、より好ましくは１６０～２３０℃である。２７０℃以下で熱酸化処理を行うことで、熱酸化処理が急激に進行することがなく、熱酸化処理をおこなったＰＰＳ樹脂を含む成形品の靭性が損なわれることがないので好ましい。一方、１６０℃以上の温度で、熱酸化処理を行うことで、適切な速度で熱酸化処理を進行させることができ、揮発成分の発生量が少ないＰＰＳ樹脂を得ることができるので好ましい。 The thermal oxidation treatment temperature of the PPS resin is preferably 160 to 270 ° C, more preferably 160 to 230 ° C. It is preferable to carry out the thermal oxidation treatment at 270 ° C. or lower because the thermal oxidation treatment does not proceed rapidly and the toughness of the molded product containing the PPS resin subjected to the thermal oxidation treatment is not impaired. On the other hand, by performing the thermal oxidation treatment at a temperature of 160 ° C. or higher, the thermal oxidation treatment can proceed at an appropriate speed, and a PPS resin with a small amount of volatile components generated can be obtained, which is preferable.
　熱酸化処理の処理時間は、０．５～３０時間が好ましく、０．５～２５時間がより好ましく、２～２０時間がさらに好ましい。処理時間を０．５時間以上とすることで十分な熱酸化処理を行うことができ揮発成分が少ないＰＰＳ樹脂を得ることができるので好ましい。処理時間を３０時間以下とすることで、熱酸化処理による架橋反応を制御することができ、熱酸化処理をおこなったＰＰＳ樹脂を含む成形品の靭性を損なうことがないので好ましい。 The treatment time of the thermal oxidation treatment is preferably 0.5 to 30 hours, more preferably 0.5 to 25 hours, and even more preferably 2 to 20 hours. It is preferable that the treatment time is 0.5 hours or more because sufficient thermal oxidation treatment can be performed and a PPS resin having a small amount of volatile components can be obtained. By setting the treatment time to 30 hours or less, the cross-linking reaction by the thermal oxidation treatment can be controlled, and the toughness of the molded product containing the PPS resin subjected to the thermal oxidation treatment is not impaired, which is preferable.
　このように熱酸化処理されたＰＰＳ樹脂は、末端基が変化すると考えられるが、熱酸化処理によって得られるＰＰＳ樹脂の構造を一般式で表すことは困難であるし、特性によって特定することも困難であるので、ＰＰＳ樹脂を得るためのプロセス（熱酸化処理）によって初めて特定が可能なものである。 It is considered that the end groups of the PPS resin subjected to the thermal oxidation treatment are changed, but it is difficult to express the structure of the PPS resin obtained by the thermal oxidation treatment by a general formula, and it is also difficult to specify by the characteristics. Therefore, it can be specified only by the process (thermal oxidation treatment) for obtaining the PPS resin.
　本発明で用いられるＰＰＳ樹脂は、真空下、３２０℃で２時間加熱溶融した際に揮発するガス発生量が０．３重量％以下であることがより好ましい。ガス発生量が０．３重量％以下であると、金型や金型ベント部に付着する揮発性成分が増加せず、転写不良やガスやけが起こりにくい。ガス発生量の下限については特に制限しないが、ガス発生量を低減する手法として挙げられるポリマー洗浄や熱酸化処理に必要な時間が長くなると経済的に不利となる。 The PPS resin used in the present invention preferably has a gas generation amount of 0.3% by weight or less when it is heated and melted at 320 ° C. for 2 hours under vacuum. When the amount of gas generated is 0.3% by weight or less, the volatile components adhering to the mold and the mold vent portion do not increase, and transfer failure and gas burning are unlikely to occur. The lower limit of the amount of gas generated is not particularly limited, but it is economically disadvantageous if the time required for polymer cleaning or thermal oxidation treatment, which is mentioned as a method for reducing the amount of gas generated, becomes long.
　なお、上記ガス発生量とは、ＰＰＳ樹脂を真空下で加熱溶融した際に揮発するガスが、冷却されて液化または固化した付着性成分の量を意味しており、ＰＰＳ樹脂を真空封入したガラスアンプルを、管状炉で加熱することにより測定されるものである。ガラスアンプルの形状としては、腹部が１００ｍｍ×２５ｍｍ、首部が２５５ｍｍ×１２ｍｍ、肉厚が１ｍｍのものを用いる。具体的な測定方法としては、ＰＰＳ樹脂を真空封入したガラスアンプルの胴部のみを３２０℃の管状炉に挿入して２時間加熱することにより、管状炉によって加熱されていないアンプルの首部で揮発性ガスが冷却されて付着する。この首部を切り出して秤量した後、付着したガスをクロロホルムに溶解して除去する。次いで、この首部を乾燥してから再び秤量する。ガスを除去した前後のアンプル首部の重量差よりガス発生量を求める。 The amount of gas generated means the amount of the adhesive component in which the gas volatilized when the PPS resin is heated and melted under vacuum is cooled and liquefied or solidified, and the glass in which the PPS resin is vacuum-sealed. The ampoule is measured by heating it in a tubular furnace. As the shape of the glass ampoule, one having an abdomen of 100 mm × 25 mm, a neck of 255 mm × 12 mm, and a wall thickness of 1 mm is used. As a specific measurement method, only the body of a glass ampoule vacuum-sealed with PPS resin is inserted into a tube furnace at 320 ° C. and heated for 2 hours, so that the ampoule is volatile at the neck of the ampoule that is not heated by the tube furnace. The gas is cooled and adheres. After cutting out the neck and weighing it, the attached gas is dissolved in chloroform and removed. The neck is then dried and then weighed again. The amount of gas generated is calculated from the weight difference between the ampoule necks before and after the gas is removed.
　上記前工程、重合反応工程、回収工程、好ましくは洗浄工程、加熱処理工程を経て得られたＰＰＳ樹脂のメルトフローレート（以下、ＭＦＲと略することもある）は１０００ｇ／１０分以上であることが好ましく、１５００ｇ／１０分以上、更に好ましくは３０００ｇ／１０分以上である。ＭＦＲが１５００ｇ／１０分以上であると、流動性に優れ成形性が良好となる。ここで、ＭＦＲは、測定温度３１５．５℃、５０００ｇ荷重とし、ＡＳＴＭ－Ｄ１２３８－７０に従って測定した値である。 The melt flow rate (hereinafter, sometimes abbreviated as MFR) of the PPS resin obtained through the above-mentioned pre-step, polymerization reaction step, recovery step, preferably washing step, and heat treatment step is 1000 g / 10 minutes or more. It is preferably 1500 g / 10 minutes or more, and more preferably 3000 g / 10 minutes or more. When the MFR is 1500 g / 10 minutes or more, the fluidity is excellent and the moldability is good. Here, MFR is a value measured according to ASTM-D1238-70 at a measurement temperature of 315.5 ° C. and a load of 5000 g.
　本発明で用いられるＰＰＳ樹脂は、５５０℃で灰化させたときの灰分率が０．３重量％以下が好ましい。灰分率が０．３重量％以下であることは、ＰＰＳ樹脂の金属含有量が適切に少ないことを意味する。金属含有量が適切に少ないと電気絶縁性に優れ、溶融流動性が良好で、耐湿熱性にも優れる。 The PPS resin used in the present invention preferably has an ash content of 0.3% by weight or less when incinerated at 550 ° C. When the ash content is 0.3% by weight or less, it means that the metal content of the PPS resin is appropriately low. When the metal content is appropriately low, the electrical insulation is excellent, the melt fluidity is good, and the moisture and heat resistance is also excellent.
　本発明で用いられるＰＰＳ樹脂は、２５０℃で２０倍重量の１－クロロナフタレンに５分間かけて溶解させ、ポアサイズ１μｍのＰＴＦＥメンブランフィルターで熱時加圧濾過した際の残渣量が４．０重量％以下であることが好ましい。残渣量が４．０重量％以下であることは、ＰＰＳ樹脂の熱酸化架橋が過度に進行せず、樹脂中のゲル化物が適切に少ないことを意味する。ＰＰＳ樹脂の熱酸化架橋を過度に進行するのを防ぐとＰＰＳ樹脂の靭性良好に保たれ、機械強度に優れる。残渣量の下限については特に制限しないが、１．５重量％以上、好ましくは１．７重量％以上である。残渣量が１．５重量％を下回ると、熱酸化架橋の程度が軽微すぎるため、溶融時の揮発成分はそれほど減少せず、揮発分低減効果が小さい可能性がある。 The PPS resin used in the present invention is dissolved in 1-chloronaphthalene having a weight of 20 times at 250 ° C. for 5 minutes, and the amount of residue when hot pressure filtration is performed with a PTFE membrane filter having a pore size of 1 μm is 4.0 weight by weight. % Or less is preferable. When the amount of the residue is 4.0% by weight or less, it means that the thermal oxidation cross-linking of the PPS resin does not proceed excessively and the gelled product in the resin is appropriately small. When the thermal oxidation cross-linking of the PPS resin is prevented from proceeding excessively, the toughness of the PPS resin is kept good and the mechanical strength is excellent. The lower limit of the residual amount is not particularly limited, but is 1.5% by weight or more, preferably 1.7% by weight or more. If the amount of the residue is less than 1.5% by weight, the degree of thermal oxidation cross-linking is too slight, so that the volatile components at the time of melting are not so reduced, and the effect of reducing the volatile content may be small.
　本発明のＰＰＳ樹脂組成物は、（Ａ）ポリフェニレンサルファイド樹脂１００重量部に対して、（Ｂ）異形断面ガラス繊維を１００～２５０重量部配合してなる。 The PPS resin composition of the present invention comprises 100 parts by weight of (A) polyphenylene sulfide resin and 100 to 250 parts by weight of (B) irregularly shaped cross-section glass fiber.
　本発明の（Ｂ）異形断面ガラス繊維は扁平形状の断面を有するガラス繊維（以下扁平ガラス繊維と略す場合がある）であり、ガラス繊維を長さ方向に直角に切断した場合の断面において、長径（断面の最長の直線距離）と短径（長径と直角方向の最長の直線距離）の比（以下扁平率と略すことがある）が１．３～１０であることが好ましい。好ましくは１．５～７、さらに好ましくは１．５～５のものである。この扁平率が１．３以上であると、樹脂組成に良好な靭性、寸法精度が備わり、１０以下であれば、樹脂組成物が良好な強度を有する。 The (B) modified cross-section glass fiber of the present invention is a glass fiber having a flat cross section (hereinafter, may be abbreviated as flat glass fiber), and has a major axis in the cross section when the glass fiber is cut at a right angle in the length direction. The ratio of (the longest linear distance in the cross section) to the minor axis (the longest linear distance in the direction perpendicular to the major axis) (hereinafter sometimes abbreviated as flatness) is preferably 1.3 to 10. It is preferably 1.5 to 7, and more preferably 1.5 to 5. When the flatness is 1.3 or more, the resin composition has good toughness and dimensional accuracy, and when it is 10 or less, the resin composition has good strength.
　扁平ガラス繊維は、その断面の長径が１０～８０μｍであることが好ましく、ガラス繊維の紡糸が容易となり、ガラス繊維の強度を高く維持することができる。より好ましくは、１５μｍ以上、５０μｍ以下である。また、その断面の短径が２～２０μｍであることが好ましく、より好ましくは４μｍ以上、１５μｍ以下である。 The major axis of the cross section of the flat glass fiber is preferably 10 to 80 μm, which facilitates spinning of the glass fiber and maintains high strength of the glass fiber. More preferably, it is 15 μm or more and 50 μm or less. The minor axis of the cross section is preferably 2 to 20 μm, more preferably 4 μm or more and 15 μm or less.
　なお、ガラス繊維断面の長径／短径の比（扁平率）は、走査型電子顕微鏡により観察し、無作為に選択した５０本のガラス繊維の断面の長径と短径を測定してその比を算出し、その数平均を算出することにより求めた値である。 The major axis / minor axis ratio (flatness) of the glass fiber cross section was observed with a scanning electron microscope, and the major axis and minor axis of the cross section of 50 randomly selected glass fibers were measured and the ratio was measured. It is a value obtained by calculating and calculating the number average.
　扁平ガラス繊維は、同等の断面積で円形状の断面形状を有するガラス繊維に比べて比表面積が大きい。また、ガラス繊維が成形品の流れ方向へ配向しやすいため、成形時のガラス繊維同士の衝突が少なく、折損がより抑制される。また、配向により、成形品の異方性がより低減される。ここで述べる異方性とは、８０ｍｍ×８０ｍｍ×３ｍｍ厚みの試験片において、樹脂の流れ方向（ＭＤ方向）と流れ方向に直角な方向（ＴＤ方向）における線膨張係数の差、ならびにその角板より切り出されて得られるＪＩＳ　Ｋ　７１６１（２０１４）に記載の試験片形状Ｔｙｐｅ　１Ｂの１／２形状における（以下半ダンベルと呼ぶことがある）クリープ変形の差をいう。クリープ変形とは引張クリープ変形において、全体の変形量から弾性変形分を除いた塑性変形分をいう。異方性が小さいということは、ＴＤ方向とＭＤ方向で線膨張係数、およびクリープ変形などの各種特性の差が小さいことを意味する。異方性が小さい樹脂組成物を用いることにより、機械強度、ウエルド強度、衝撃強度および高温剛性に優れる成形品を得ることができる。 Flat glass fiber has a larger specific surface area than glass fiber having a circular cross-sectional shape with the same cross-sectional area. In addition, since the glass fibers are easily oriented in the flow direction of the molded product, there is less collision between the glass fibers during molding, and breakage is further suppressed. In addition, the orientation further reduces the anisotropy of the molded product. The anisotropy described here is the difference in the coefficient of linear expansion in the resin flow direction (MD direction) and the direction perpendicular to the flow direction (TD direction) in a test piece having a thickness of 80 mm × 80 mm × 3 mm, and the square plate thereof. It refers to the difference in creep deformation (hereinafter sometimes referred to as a half dumbbell) in the 1/2 shape of the test piece shape Type 1B described in JIS K 7161 (2014) obtained by cutting out. Creep deformation refers to the plastic deformation amount obtained by subtracting the elastic deformation amount from the total deformation amount in the tensile creep deformation. The small anisotropy means that the difference in various characteristics such as the coefficient of linear expansion and creep deformation is small in the TD direction and the MD direction. By using a resin composition having a small anisotropy, it is possible to obtain a molded product having excellent mechanical strength, weld strength, impact strength and high temperature rigidity.
　本発明に用いる（Ｂ）異形断面ガラス繊維の配合量は、上記（Ａ）ポリフェニレンサルファイド樹脂１００重量部に対して、１００～２５０重量部である。（Ａ）ポリフェニレンサルファイド樹脂１００重量部に対して、（Ｂ）異形断面ガラス繊維が１００重量部未満では異方性による差が発生する。好ましくは１１０重量部以上である。（Ａ）ポリフェニレンサルファイド樹脂１００重量部に対して、（Ｂ）異形断面ガラス繊維が２５０重量を超えると流動性が損なわれ、成形性に影響を及ぼす。好ましくは２２０重量部以下である。 The blending amount of the (B) modified cross-section glass fiber used in the present invention is 100 to 250 parts by weight with respect to 100 parts by weight of the above (A) polyphenylene sulfide resin. If the amount of (B) irregularly shaped cross-section glass fiber is less than 100 parts by weight with respect to 100 parts by weight of (A) polyphenylene sulfide resin, a difference due to anisotropy occurs. It is preferably 110 parts by weight or more. If the amount of (B) modified cross-section glass fiber exceeds 250 weight with respect to 100 parts by weight of (A) polyphenylene sulfide resin, the fluidity is impaired and the moldability is affected. It is preferably 220 parts by weight or less.
　本発明のポリフェニレンサルファイド樹脂組成物は（Ａ）ポリフェニレンサルファイド樹脂に対して、（Ｃ）非繊維系無機フィラーを２５～１５０重量部配合してなる。 The polyphenylene sulfide resin composition of the present invention comprises (A) a polyphenylene sulfide resin mixed with (C) 25 to 150 parts by weight of a non-fiber-based inorganic filler.
　ここで、（Ｃ）非繊維系無機フィラーは、以下の（Ｃ－ａ）および（Ｃ－ｂ）を満たすことを特徴とする。
（Ｃ－ａ）モース硬度が２を超え４未満
（Ｃ－ｂ）融点もしくは軟化点が３８０℃以上
　上記モース硬度とは、１０段階モース硬度を意味する。モース硬度が２以下の場合、同時に混錬される異形断面ガラスによって変形が生じてしまい寸法安定性が悪化する。また、４以上の場合は、成形機等の加工治具の摩耗を促進してしまう。好ましいモース硬度は、２．５を超え４未満である。なお、本発明において、モース硬度は、非繊維系無機フィラーとして使用される形状（粒状）とする前段階の、ある程度の塊状態において測定したモース硬度の値を「（Ｃ）非繊維系無機フィラーのモース硬度」とする。 Here, the non-fiber-based inorganic filler (C) is characterized by satisfying the following (Ca) and (Cb).
(Ca) Mohs hardness is more than 2 and less than 4 (Cb) Melting point or softening point is 380 ° C. or more The above Mohs hardness means 10-step Mohs hardness. When the Mohs hardness is 2 or less, deformation occurs due to the irregular cross-section glass that is kneaded at the same time, and the dimensional stability deteriorates. Further, when it is 4 or more, the wear of the processing jig such as a molding machine is promoted. The preferred Mohs hardness is greater than 2.5 and less than 4. In the present invention, the Mohs hardness is the value of the Mohs hardness measured in a lump state to some extent before the shape (granular) used as the non-fiber-based inorganic filler is set to "(C) Non-fiber-based inorganic filler. Mohs hardness of.
　ＰＰＳ樹脂の加工温度は３００～３４０℃であり、樹脂にせん断力が掛かることによって、樹脂温度が３８０℃以上になることがある。そのため寸法安定性に寄与する非繊維系無機フィラーにはその加工温度においても形状の安定性が求められることから、（Ｃ）非繊維系無機フィラーは３８０℃以上の融点もしくは軟化点を有することが必要であり、４００℃以上の融点もしくは軟化点を有することが好ましい。融点もしくは軟化点の上限値については特には定めないが、非繊維系無機フィラーとして実用性がある種類のものとしては２，０００℃程度である。ここで融点もしくは軟化点は示差走査熱量（ＤＳＣ）を用いて測定した値で定義される。 The processing temperature of the PPS resin is 300 to 340 ° C, and the resin temperature may reach 380 ° C or higher due to the application of shearing force to the resin. Therefore, since the non-fiber-based inorganic filler that contributes to dimensional stability is required to have shape stability even at the processing temperature, (C) the non-fiber-based inorganic filler may have a melting point or a softening point of 380 ° C. or higher. It is necessary and preferably has a melting point or softening point of 400 ° C. or higher. The upper limit of the melting point or the softening point is not particularly defined, but is about 2,000 ° C. as a practical type of non-fiber-based inorganic filler. Here, the melting point or softening point is defined by a value measured using differential scanning calorimetry (DSC).
　かかる（Ｃ）非繊維系無機フィラーの具体例としては、マイカ、炭酸カルシウム、炭酸マグネシウム、ドロマイトなどの炭酸塩、硫酸カルシウム、硫酸バリウムなどの硫酸塩などの非繊維状の充填材が用いられ、これらは中空であってもよく、さらにはこれら非繊維系無機フィラーを２種類以上併用することも可能である。また、これらの非繊維系無機フィラーをイソシアネート系化合物、有機シラン系化合物、有機チタネート系化合物、有機ボラン系化合物およびエポキシ化合物などのカップリング剤で予備処理して使用してもよい。 As a specific example of the (C) non-fiber-based inorganic filler, a non-fibrous filler such as a carbonate such as mica, calcium carbonate, magnesium carbonate or dolomite, or a sulfate such as calcium sulfate or barium sulfate is used. These may be hollow, and two or more kinds of these non-fiber-based inorganic fillers can be used in combination. Further, these non-fiber inorganic fillers may be pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound and an epoxy compound before use.
　中でも材料の熱膨張低減の観点から、マイカおよび炭酸カルシウムから選択される少なくとも１種であることが好ましく、異方性低減の観点から炭酸カルシウムであることが好ましい。 Among them, at least one selected from mica and calcium carbonate is preferable from the viewpoint of reducing the thermal expansion of the material, and calcium carbonate is preferable from the viewpoint of reducing anisotropy.
　また、本発明の（Ｃ）非繊維系無機フィラーは、六方晶窒化ホウ素、水酸化マグネシウム、タルク、酸化マグネシウム、および窒化アルミニウムを除く。 Further, the (C) non-fiber-based inorganic filler of the present invention excludes hexagonal boron nitride, magnesium hydroxide, talc, magnesium oxide, and aluminum nitride.
　本発明のＰＰＳ樹脂組成物における（Ｃ）非繊維系無機フィラーの配合量は、（Ａ）ＰＰＳ樹脂１００重量部に対して、（Ｃ）非繊維系無機フィラー２５～１５０重量部からなり、好ましくは３０重量部～１３０重量部である。 The blending amount of (C) non-fiber-based inorganic filler in the PPS resin composition of the present invention is preferably 25 to 150 parts by weight of (C) non-fiber-based inorganic filler with respect to 100 parts by weight of (A) PPS resin. Is 30 parts by weight to 130 parts by weight.
　更に、本発明においては、（Ｂ）異形断面ガラス繊維と、（Ｃ）非繊維系無機フィラーとを併用して用いることが、優れた低異方性を発現するうえで必要である。本発明は、（Ａ）ポリフェニレンサルファイド樹脂１００重量部に対する、（Ｂ）異形断面ガラス繊維の配合重量Ｘと（Ｃ）非繊維系無機フィラーの配合重量Ｙとの比率Ｘ／Ｙが１より大きく７未満である。好ましくは１より大きく５未満である。比率Ｘ／Ｙが１以下である場合、つまりは（Ｂ）異形断面ガラス繊維と（Ｃ）非繊維系無機フィラーの配合重量が同じであるか、（Ｂ）異形断面ガラス繊維の配合重量が（Ｃ）非繊維系無機フィラーの配合重量よりも少ない場合は、成形品の異方性を制御できず、さらには湿熱膨張時の寸法変化が著しく大きくなる。一方で比率Ｘ／Ｙが７以上、つまりは（Ｂ）異形断面ガラス繊維の配合重量が非常に多く、（Ｃ）非繊維系無機フィラーの配合重量が少ない場合は、異形断面ガラスの影響が強くなり、線膨張係数が増加し、さらに低異方性が失われる。 Further, in the present invention, it is necessary to use (B) a modified cross-section glass fiber and (C) a non-fiber-based inorganic filler in combination in order to exhibit excellent low anisotropy. In the present invention, the ratio X / Y of (B) the compounding weight X of the modified cross-section glass fiber to (C) the compounding weight Y of the non-fiber-based inorganic filler with respect to 100 parts by weight of the polyphenylene sulfide resin is larger than 1 and 7 Is less than. It is preferably greater than 1 and less than 5. When the ratio X / Y is 1 or less, that is, the compounding weight of (B) the modified cross-sectional glass fiber and (C) the non-fiber-based inorganic filler is the same, or (B) the compounding weight of the modified cross-sectional glass fiber is (B). C) If it is less than the blending weight of the non-fiber-based inorganic filler, the anisotropy of the molded product cannot be controlled, and the dimensional change during moist heat expansion becomes significantly large. On the other hand, when the ratio X / Y is 7 or more, that is, when (B) the blended weight of the irregular cross-section glass fiber is very large and (C) the blended weight of the non-fiber-based inorganic filler is small, the influence of the irregular cross-section glass is strong. As a result, the coefficient of linear expansion increases and the low anisotropy is lost.
　更に、本発明のＰＰＳ樹脂組成物には、機械的強度、靱性などの向上を目的に、エポキシ基、アミノ基、イソシアネート基、水酸基、メルカプト基およびウレイド基の中から選ばれた少なくとも１種の官能基を有するアルコキシシラン化合物を添加することが好ましい。かかる化合物の具体例としては、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリエトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシランなどのエポキシ基含有アルコキシシラン化合物、γ－メルカプトプロピルトリメトキシシラン、γ－メルカプトプロピルトリエトキシシランなどのメルカプト基含有アルコキシシラン化合物、γ－ウレイドプロピルトリエトキシシラン、γ－ウレイドプロピルトリメトキシシラン、γ－（２－ウレイドエチル）アミノプロピルトリメトキシシランなどのウレイド基含有アルコキシシラン化合物、γ－イソシアネートプロピルトリエトキシシラン、γ－イソシアネートプロピルトリメトキシシラン、γ－イソシアネートプロピルメチルジメトキシシラン、γ－イソシアネートプロピルメチルジエトキシシラン、γ－イソシアネートプロピルエチルジメトキシシラン、γ－イソシアネートプロピルエチルジエトキシシラン、γ－イソシアネートプロピルトリクロロシランなどのイソシアネート基含有アルコキシシラン化合物、γ－（２－アミノエチル）アミノプロピルメチルジメトキシシラン、γ－（２－アミノエチル）アミノプロピルトリメトキシシラン、γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシランなどのアミノ基含有アルコキシシラン化合物、およびγ－ヒドロキシプロピルトリメトキシシラン、γ－ヒドロキシプロピルトリエトキシシランなどの水酸基含有アルコキシシラン化合物などが挙げられる。なかでもエポキシ基、アミノ基、イソシアネート基、水酸基を有するアルコキシシランが優れたウエルド強度を得る上で特に好適である。かかるシラン化合物の好適な添加量は、（Ａ）ＰＰＳ樹脂１００重量部に対し、０．１～３重量部の範囲が選択される。 Further, the PPS resin composition of the present invention has at least one selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group and a ureido group for the purpose of improving mechanical strength and toughness. It is preferable to add an alkoxysilane compound having a functional group. Specific examples of such compounds include epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. , Γ-Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane and other mercapto group-containing alkoxysilane compounds, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) amino Ureid group-containing alkoxysilane compounds such as propyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, γ-isocyanatepropyl Isocyanate group-containing alkoxysilane compounds such as ethyldimethoxysilane, γ-isocyanatepropylethyldiethoxysilane, γ-isocyanatepropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) Amino group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane, and hydroxyl groups such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. Examples thereof include alkoxysilane compounds. Of these, an alkoxysilane having an epoxy group, an amino group, an isocyanate group, and a hydroxyl group is particularly suitable for obtaining excellent weld strength. A suitable amount of the silane compound added is selected in the range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the (A) PPS resin.
　本発明のＰＰＳ樹脂組成物は、本発明の効果を損なわない範囲において、更に（Ｄ）（Ａ）ＰＰＳ樹脂以外の他の樹脂（以下、（Ｄ）その他の樹脂と略す場合がある）をブレンドして用いてもよい。かかるブレンド可能な樹脂には特に制限はないが、その具体例としては、ナイロン６，ナイロン６６，ナイロン６１０、ナイロン１１、ナイロン１２、芳香族系ナイロンなどのポリアミド、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリシクロヘキシルジメチレンテレフタレート、ポリナフタレンテレフタレートなどのポリエステル樹脂、ポリエチレン、ポリプロピレン、ポリテトラフルオロエチレン、ポリオレフィン系エラストマー、ポリエーテルエステルエラストマー、ポリエーテルアミドエラストマー、ポリアミドイミド、ポリアセタール、ポリイミド、ポリフェニレンエーテル、ポリエーテルイミド、ポリエーテルスルホン、ポリサルフォン樹脂、ポリアリルサルフォン樹脂、ポリケトン樹脂、ポリアリレート樹脂、液晶ポリマー、ポリエーテルケトン樹脂、ポリチオエーテルケトン樹脂、ポリエーテルエーテルケトン樹脂、ポリアミドイミド樹脂、四フッ化ポリエチレン樹脂、エポキシ基含有ポリオレフィン共重合体、ビスフェノールＡ型などのビスフェノールエポキシ樹脂、ノボラックフェノール型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂などが挙げられる。特に、ＰＰＳ樹脂のガラス転移温度（約８０℃）以上での熱変形を抑制することを目的として、ポリイミド、ポリフェニレンエーテル、ポリエーテルイミド、ポリエーテルスルホンが望ましい。かかる（Ｄ）その他の樹脂の好適な添加量は、（Ａ）ＰＰＳ樹脂１００重量部に対し、０～２０重量部の範囲が選択される。 The PPS resin composition of the present invention is further blended with a resin other than (D) (A) PPS resin (hereinafter, may be abbreviated as (D) other resin) as long as the effect of the present invention is not impaired. May be used. The blendable resin is not particularly limited, and specific examples thereof include polyamides such as nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, and aromatic nylon, polyethylene terephthalate, polybutylene terephthalate, and poly. Polyester resins such as cyclohexyldimethylene terephthalate and polynaphthalene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene, polyolefin-based elastomers, polyether ester elastomers, polyetheramide elastomers, polyamideimides, polyacetals, polyimides, polyphenylene ethers, polyetherimides, Polyether sulfone, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyether ketone resin, polythioether ketone resin, polyether ether ketone resin, polyamideimide resin, tetrafluoride polyethylene resin, epoxy Examples thereof include a group-containing polyolefin copolymer, a bisphenol epoxy resin such as bisphenol A type, a novolak phenol type epoxy resin, and a cresol novolak type epoxy resin. In particular, polyimide, polyphenylene ether, polyetherimide, and polyether sulfone are desirable for the purpose of suppressing thermal deformation of the PPS resin at a glass transition temperature (about 80 ° C.) or higher. A suitable amount of the (D) other resin added is selected in the range of 0 to 20 parts by weight with respect to 100 parts by weight of the (A) PPS resin.
　なお、本発明のＰＰＳ樹脂組成物には、本発明の効果を損なわない範囲で他の成分、例えば前記以外の酸化防止剤や耐熱安定剤（ヒドロキノン系）、耐候剤（レゾルシノール系、サリシレート系、ベンゾトリアゾール系、ベンゾフェノン系、ヒンダードアミン系等）、離型剤および滑剤（モンタン酸およびその金属塩、そのエステル、そのハーフエステル、ステアリルアルコール、ステアラミド、ビス尿素およびポリエチレンワックス等）、顔料（硫化カドミウム、フタロシアニン、着色用カーボンブラック等）、染料（ニグロシン等）、可塑剤（ｐ－オキシ安息香酸オクチル、Ｎ－ブチルベンゼンスルホンアミド等）、帯電防止剤（アルキルサルフェート型アニオン系帯電防止剤、４級アンモニウム塩型カチオン系帯電防止剤、ポリオキシエチレンソルビタンモノステアレートのような非イオン系帯電防止剤、ベタイン系両性帯電防止剤等）、難燃剤（例えば、赤燐、燐酸エステル、メラミンシアヌレート、ポリリン酸アンモニウム、臭素化ポリスチレン、臭素化ポリフェニレンエーテル、臭素化ポリカーボネート、臭素化エポキシ樹脂あるいはこれらの臭素系難燃剤と三酸化アンチモンとの組み合わせ等）、熱安定剤、ステアリン酸カルシウム、ステアリン酸アルミニウム、ステアリン酸リチウムなどの滑剤、紫外線防止剤、着色剤、難燃剤および発泡剤などの通常の添加剤を添加することができる。 The PPS resin composition of the present invention contains other components, such as antioxidants, heat-resistant stabilizers (hydroquinone-based), and weather-resistant agents (resorcinol-based, salicylate-based), as long as the effects of the present invention are not impaired. Bentriazole-based, benzophenone-based, hindered amine-based, etc.), antistatic agents and lubricants (montanic acid and its metal salts, their esters, their half esters, stearic acid, stearamide, bisurea and polyethylene wax, etc.), pigments (cadmium sulfide, Phthalocyanin, carbon black for coloring, etc.), dyes (niglosin, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agents (alkylsulfate-type anionic antistatic agents, quaternary ammonium Salt-type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents, etc.), flame retardants (eg, red phosphorus, phosphate ester, melamine cyanurate, polyphosphorus) Ammonium acid, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin or a combination of these brominated flame retardants and antimon trioxide, etc.), heat stabilizer, calcium stearate, aluminum stearate, stearic acid Ordinary additives such as lubricants such as lithium, UV inhibitors, colorants, flame retardants and foaming agents can be added.
　本発明のＰＰＳ樹脂組成物の調製方法には特に制限はないが、各原料を単軸あるいは２軸の押出機、バンバリーミキサー、ニーダーおよびミキシングロールなど通常公知の溶融混合機に供給して、２８０～３８０℃の温度で混練する方法などを代表例として挙げることができる。原料の混合順序にも特に制限はなく、全ての原材料を配合後上記の方法により溶融混練する方法、一部の原材料を配合後上記の方法により溶融混練し、更に残りの原材料を配合し溶融混練する方法、あるいは一部の原材料を配合後単軸あるいは２軸の押出機により溶融混練中にサイドフィーダーを用いて残りの原材料を混合する方法などのいずれの方法を用いてもよい。また、少量添加剤成分については、他の成分を上記の方法などで混練しペレット化した後、成形前に添加して成形に供することももちろん可能である。 The method for preparing the PPS resin composition of the present invention is not particularly limited, but each raw material is supplied to a commonly known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader and a mixing roll, and 280. A typical example is a method of kneading at a temperature of about 380 ° C. The mixing order of the raw materials is not particularly limited, and all the raw materials are blended and then melt-kneaded by the above method, some raw materials are blended and then melt-kneaded by the above method, and the remaining raw materials are blended and melt-kneaded. Any method may be used, such as a method of mixing some raw materials and then mixing the remaining raw materials using a side feeder during melt-kneading with a single-screw or twin-screw extruder. Further, as for the small amount additive component, it is of course possible to knead other components by the above method or the like to pelletize them, and then add them before molding and use them for molding.
　以下に実施例を示し、本発明を更に具体的に説明するが、本発明はこれら実施例の記載に限定されるものではない。 Examples are shown below, and the present invention will be described in more detail, but the present invention is not limited to the description of these examples.
　［製造したＰＰＳ樹脂の評価方法］
　（１）メルトフローレート（ＭＦＲ）
測定温度３１５．５℃、５０００ｇ荷重とし、ＡＳＴＭ－Ｄ１２３８－７０に準ずる方法で測定した。 [Evaluation method of manufactured PPS resin]
(1) Melt flow rate (MFR)
The measurement temperature was 315.5 ° C. and a load of 5000 g, and the measurement was carried out by a method according to ASTM-D1238-70.
　但し、粘度が低いポリフェニレンサルファイド樹脂に関しては、次の方法でＭＦＲを算出した。ポリフェニレンサルファイド樹脂を測定温度３１５．５℃、３４５ｇ荷重とし、ＡＳＴＭ－Ｄ１２３８－７０に準ずる方法でＥＲを測定し、下記式［Ｉ］によりＭＦＲの値を算出した。 However, for polyphenylene sulfide resin with low viscosity, MFR was calculated by the following method. The polyphenylene sulfide resin was measured at a measurement temperature of 315.5 ° C. and a load of 345 g, ER was measured by a method according to ASTM-D1238-70, and the value of MFR was calculated by the following formula [I].
　ＭＦＲ＝１５．８×４．４×ＥＲ　　［Ｉ］
　（２）残渣量
　空圧キャップと採集ロートを具備した（株）センシュー科学製のＳＵＳ試験管に、予め秤量しておいたポアサイズ１μｍのＰＴＦＥメンブランフィルターをセットし、約８０μｍ厚にプレスフィルム化したＰＰＳ樹脂１００ｍｇおよび１－クロロナフタレン２ｇを計り入れてから密閉した。これをセンシュー科学製の高温濾過装置ＳＳＣ－９３００に挿入し、２５０℃で５分間加熱振とうしてＰＰＳ樹脂を１－クロロナフタレンに溶解した。空気を含んだ２０ｍＬの注射器を空圧キャップに接続した後、ピストンを押出して溶液をメンブランフィルターで濾過した。メンブランフィルターを取り出し、１５０℃で１時間真空乾燥してから秤量した。プレスフィルム化したＰＰＳの仕込み重量に対する濾過前後のメンブランフィルター重量の差を残渣量（重量％）とした。 MFR = 15.8 x 4.4 x ER [I]
(2) Residue amount A pre-weighed 1 μm-sized PTFE membrane filter was set in a SUS test tube manufactured by Senshu Kagaku Co., Ltd. equipped with a pneumatic cap and a collection funnel, and a press film was formed to a thickness of about 80 μm. 100 mg of PPS resin and 2 g of 1-chloronaphthalene were weighed and then sealed. This was inserted into a high-temperature filtration device SSC-9300 manufactured by Senshu Kagaku, and the PPS resin was dissolved in 1-chloronaphthalene by heating and shaking at 250 ° C. for 5 minutes. After connecting a 20 mL syringe containing air to the pneumatic cap, the piston was extruded and the solution was filtered through a membrane filter. The membrane filter was taken out, vacuum dried at 150 ° C. for 1 hour, and then weighed. The difference in the weight of the membrane filter before and after filtration with respect to the charged weight of the pressed PPS was defined as the residual amount (% by weight).
　[参考例]
　撹拌機および底栓弁付きの７０リットルオートクレーブに、４７．５％水硫化ナトリウム８．２７ｋｇ（７０．００モル）、９６％水酸化ナトリウム２．９１ｋｇ（６９．８０モル）、Ｎ－メチル－２－ピロリドン（以下、ＮＭＰ）１１．４５ｋｇ（１１５．５０モル）、及びイオン交換水１０．５ｋｇを仕込み、常圧で窒素を通じながら２４５℃まで約３時間かけて徐々に加熱し、水１４．７８ｋｇおよびＮＭＰ０．２８ｋｇを留出した後、反応容器を２００℃に冷却した。仕込みアルカリ金属硫化物１モル当たりの系内残存水分量は、ＮＭＰの加水分解に消費された水分を含めて１．０６モルであった。また、硫化水素の飛散量は、仕込みアルカリ金属硫化物１モル当たり０．０２モルであった。 [Reference example]
8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.91 kg (69.80 mol) of 96% sodium hydroxide, N-methyl-2 in a 70 liter autoclave with a stirrer and bottom plug valve. -Pyrrolidone (hereinafter, NMP) 11.45 kg (115.50 mol) and ion-exchanged water 10.5 kg were charged, and gradually heated to 245 ° C. over about 3 hours while passing nitrogen under normal pressure, and 14.78 kg of water. After distilling 0.28 kg of NMP and NMP, the reaction vessel was cooled to 200 ° C. The amount of residual water in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.
　その後２００℃まで冷却し、ｐ－ジクロロベンゼン１０．４８ｋｇ（７１．２７モル）、ＮＭＰ９．３７ｋｇ（９４．５０モル）を加え、反応容器を窒素ガス下に密封し、２４０ｒｐｍで撹拌しながら０．６℃／分の速度で２００℃から２７０℃まで昇温した。２７０℃で１００分反応した後、オートクレーブの底栓弁を開放し、窒素で加圧しながら内容物を攪拌機付き容器に１５分かけてフラッシュし、２５０℃でしばらく撹拌して大半のＮＭＰを除去した。 After that, the mixture was cooled to 200 ° C., 10.48 kg (71.27 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and the reaction vessel was stirred at 240 rpm. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 6 ° C./min. After reacting at 270 ° C. for 100 minutes, the bottom valve of the autoclave was opened, the contents were flushed into a container with a stirrer for 15 minutes while pressurizing with nitrogen, and the contents were stirred at 250 ° C. for a while to remove most of NMP. ..
　得られた固形物およびイオン交換水７６リットルを撹拌機付きオートクレーブに入れ、７０℃で３０分洗浄した後、ガラスフィルターで吸引濾過した。次いで７０℃に加熱した７６リットルのイオン交換水をガラスフィルターに注ぎ込み、吸引濾過してケークを得た。 The obtained solid matter and 76 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70 ° C. for 30 minutes, and then suction-filtered with a glass filter. Then, 76 liters of ion-exchanged water heated to 70 ° C. was poured into a glass filter and suction filtered to obtain a cake.
　得られたケークおよびイオン交換水９０リットルを撹拌機付きオートクレーブに仕込み、ｐＨが７になるよう酢酸を添加した。オートクレーブ内部を窒素で置換した後、１９２℃まで昇温し、３０分保持した。その後オートクレーブを冷却して内容物を取り出した。 90 liters of the obtained cake and ion-exchanged water were placed in an autoclave with a stirrer, and acetic acid was added so that the pH became 7. After replacing the inside of the autoclave with nitrogen, the temperature was raised to 192 ° C. and held for 30 minutes. The autoclave was then cooled and the contents were removed.
　内容物をガラスフィルターで吸引濾過した後、これに７０℃のイオン交換水７６リットルを注ぎ込み吸引濾過してケークを得た。得られたケークを窒素気流下、１２０℃で乾燥することにより、乾燥ＰＰＳを得た。得られたＰＰＳは、ＥＲが９０ｇ／１０分であり、ＭＦＲに換算すると、６２５７ｇ／１０分、残渣量が１．２重量％であった。 After suction-filtering the contents with a glass filter, 76 liters of ion-exchanged water at 70 ° C. was poured into the contents and suction-filtered to obtain a cake. The obtained cake was dried at 120 ° C. under a nitrogen stream to obtain a dried PPS. The obtained PPS had an ER of 90 g / 10 minutes, converted to MFR of 6257 g / 10 minutes, and a residual amount of 1.2% by weight.
　実施例および比較例に用いられる原料を以下に示す。
（Ａ）ＰＰＳ樹脂
ＰＰＳ：参考例に記載の方法で重合したＰＰＳ樹脂
（Ｂ）異形断面ガラス繊維
扁平ガラス繊維：ＥＣＳ－０３－９７１ＥＷ（日本電気硝子（株）製、扁平率＝４）
（Ｃ）非繊維系無機フィラー
Ｃ－１：重質炭酸カルシウム（（株）カルファイン製　ＫＳＳ－１０００）、モース硬度：３、融点：８２℃(分解)
Ｃ－２：タルク（林化成（株）製　ＰＫ－Ｓ）、モース硬度：１、融点：＞４５０℃（分解）
（Ｄ）その他樹脂
Ｄ－１：ポリエーテルスルホン（住友化学（株）製、スミカエクセル３６００Ｐ）
Ｄ－２：ポリエーテルイミド（ＳＡＢＩＣ社製、ウルテム１０１０）
Ｄ－３：ポリフェニレンエーテル（旭化成（株）製、ＸＹＲＯＳ２０２Ａ）
（Ｂ’）繊維状充填材（比較例：本発明の（Ｂ）成分に該当しないガラス繊維）
Ｂ’－１：チョップドストランド（日本電気硝子（株）製、Ｔ－７１７、平均繊維径：１３μｍ、扁平率＝１）
Ｂ’－２：チョップドストランド（日本電気硝子（株）製、Ｔ－７４７Ｈ、平均繊維径：１３μｍ、扁平率＝１）。 The raw materials used in Examples and Comparative Examples are shown below.
(A) PPS resin PPS: PPS resin polymerized by the method described in the reference example (B) Deformed cross-section glass fiber Flat glass fiber: ECS-03-971EW (manufactured by Nippon Electric Glass Co., Ltd., flatness = 4)
(C) Non-fiber-based inorganic filler C-1: Heavy calcium carbonate (KSS-1000 manufactured by Calfine Co., Ltd.), Mohs hardness: 3, melting point: 82 ° C. (decomposition)
C-2: Talc (PK-S manufactured by Hayashi Kasei Co., Ltd.), Mohs hardness: 1, melting point:> 450 ° C (decomposition)
(D) Other resin D-1: Polyether sulfone (manufactured by Sumitomo Chemical Co., Ltd., Sumika Excel 3600P)
D-2: Polyetherimide (manufactured by SABIC, Ultem 1010)
D-3: Polyphenylene ether (manufactured by Asahi Kasei Corporation, XYROS202A)
(B') Fibrous filler (Comparative example: glass fiber not corresponding to the component (B) of the present invention)
B'-1: Chopped strand (manufactured by Nippon Electric Glass Co., Ltd., T-717, average fiber diameter: 13 μm, flatness = 1)
B'-2: Chopped strand (manufactured by Nippon Electric Glass Co., Ltd., T-747H, average fiber diameter: 13 μm, flatness = 1).
　［測定評価方法］
　本実施例および比較例における測定評価方法は以下の通りである。 [Measurement evaluation method]
The measurement and evaluation methods in this example and the comparative example are as follows.
　（曲げ強度、曲げ弾性率の測定）
　ＩＳＯ１７８（２００１）に準じて測定を行った。具体的には次のように測定を行った。樹脂組成物ペレットを、シリンダー温度３１０℃、金型温度１４５℃に設定した住友重機械工業（株）製射出成形機（ＳＥ５０ＤＵＺ－Ｃ１６０）に供給し、充填時間０．８ｓで充填、充填圧力の７５％の保圧にて射出成形を行い、ＩＳＯ ２０７５３（２００８）に規定されるタイプＢ２試験片形状を得た。この試験片を、２３℃、相対湿度５０％の条件で１６時間状態調節を行った後、２３℃、相対湿度５０％の雰囲気下、スパン６４ｍｍ、歪み速度２ｍｍ/ｍｉｎの条件で測定を行った。 (Measurement of bending strength and flexural modulus)
The measurement was performed according to ISO178 (2001). Specifically, the measurement was performed as follows. The resin composition pellets are supplied to an injection molding machine (SE50DUZ-C160) manufactured by Sumitomo Heavy Industries, Ltd., which has a cylinder temperature of 310 ° C. and a mold temperature of 145 ° C., and is filled with a filling time of 0.8 s. Injection molding was performed with a holding pressure of 75% to obtain a type B2 test piece shape specified in ISO 20753 (2008). This test piece was adjusted for 16 hours under the conditions of 23 ° C. and 50% relative humidity, and then measured under the conditions of 23 ° C. and 50% relative humidity, a span of 64 mm, and a strain rate of 2 mm / min. ..
　（線膨張係数）
　ＰＰＳ樹脂の線膨張係数の測定においては、図１に示す一辺ＳＬが８０ｍｍの正方形で、厚みＤが３ｍｍの、試験片作成のための切削加工用平板４から、樹脂流れ方向ＭＤ、および樹脂流れ方向に対して直角方向ＴＤをそれぞれ長さ方向として、図３に示す幅Ｗが５ｍｍ、長さＬが１０ｍｍ、厚みＤが３ｍｍの試験片を、図２に示す位置から切削加工によって切り出すことで作製した試験片５および試験片６を用いた。なお、前記切削加工用平板４は日精樹脂工業（株）製射出成形機ＮＥＸ－１０００－９Ｅを用い、シリンダ温度：３２０℃、射出圧力：成形下限圧力＋１２．８ＭＰａ、射出時間：１５ｓｅｃ、冷却時間：１５ｓｅｃの条件で射出成形によって作製した。 (Coefficient of linear expansion)
In the measurement of the linear expansion coefficient of the PPS resin, the resin flow direction MD and the resin flow are measured from the cutting flat plate 4 for preparing a test piece, which is a square having a side SL of 80 mm and a thickness D of 3 mm shown in FIG. A test piece having a width W of 5 mm, a length L of 10 mm, and a thickness D of 3 mm shown in FIG. 3 is cut out from the position shown in FIG. 2 by cutting with the TD in the direction perpendicular to the direction as the length direction. The prepared test piece 5 and test piece 6 were used. The flat plate 4 for cutting uses an injection molding machine NEX-1000-9E manufactured by Nissei Jushi Kogyo Co., Ltd., cylinder temperature: 320 ° C., injection pressure: lower limit molding pressure + 12.8 MPa, injection time: 15 sec, cooling time. : Made by injection molding under the condition of 15 sec.
　図１（ａ）は上記試験片作成のための切削加工用平板４の平面図であり、図１（ｂ）は同切削加工用平板４の側面図である。この線膨張係数試験片作成のための切削加工用平板４はスプルー１、ランナー２、ゲート３を有し、図２に示す位置を切削加工して図３に示す形状の試験片５，６を作製した。図３（ａ）は試験片５，６の平面図であり、図３（ｂ）は試験片５，６の側面図である。 FIG. 1A is a plan view of the cutting flat plate 4 for producing the test piece, and FIG. 1B is a side view of the cutting flat plate 4 for creating the test piece. The cutting flat plate 4 for producing the linear expansion coefficient test piece has a sprue 1, a runner 2, and a gate 3, and the test pieces 5 and 6 having the shape shown in FIG. 3 are cut at the positions shown in FIG. Made. FIG. 3A is a plan view of the test pieces 5 and 6, and FIG. 3B is a side view of the test pieces 5 and 6.
　線膨張係数はセイコー電子工業（株）製ＴＭＡ－１００を用いて、負荷荷重２ｇ、－５０℃～２００℃の温度領域を５℃／分の速度で昇温し、－４０℃～１５０℃の温度範囲における数値で表した。 The coefficient of linear expansion is TMA-100 manufactured by Seiko Electronics Co., Ltd., and the temperature range of -50 ° C to 200 ° C is raised at a rate of 5 ° C / min with a load load of 2 g, and the linear expansion coefficient is -40 ° C to 150 ° C. It was expressed numerically in the temperature range.
　（膨潤性）
　ＰＰＳ樹脂の膨潤性評価は、線膨張係数の測定において作成した試験片と全く同じ条件で射出成形によって作製した。 (Swelling)
The swellability evaluation of the PPS resin was prepared by injection molding under exactly the same conditions as the test piece prepared in the measurement of the coefficient of linear expansion.
　この試験片について、温度８５℃、湿度８５％ＲＨの高温高湿内で１，０００ｈｒ処理したのちの、ＭＤ方向とＴＤ方向の膨張率を測定した。膨張率は以下の式（２）で表される。 This test piece was treated for 1,000 hr in a high temperature and high humidity of 85 ° C. and 85% humidity, and then the expansion coefficient in the MD direction and the TD direction was measured. The expansion coefficient is expressed by the following equation (2).
　膨張率（％）＝［処理後寸法（ｍｍ）－初期寸法（ｍｍ）］／初期寸法（ｍｍ）×１００　　（２）
　なお、寸法の測定位置は、図１の切削加工用平板４内に記載した各矢印に示すとおり、各ＭＤ方向、ＴＤ方向の中心線とした。 Expansion rate (%) = [Post-processed dimensions (mm) -Initial dimensions (mm)] / Initial dimensions (mm) x 100 (2)
The measurement position of the dimension was set to the center line in each MD direction and TD direction as shown by each arrow described in the cutting flat plate 4 of FIG.
　（クリープ変形性）
　ＰＰＳ樹脂のクリープ変形性評価は、図１に示す一辺ＳＬが８０ｍｍの正方形で、厚みＤが３ｍｍの、試験片作成のための切削加工用平板４から、樹脂流れ方向ＭＤ、および樹脂流れ方向に対して直角方向ＴＤとし、それぞれの方向におけるクリープ変形性評価試験ができるように、図２の５，６に示す位置からＪＩＳ　Ｋ　７１６１（２０１４）に記載の試験片形状Ｔｙｐｅ　１Ｂの１／２形状（半ダンベル）に切削した試験片を使用した。 (Creep deformation)
The creep deformation evaluation of the PPS resin was carried out from the cutting flat plate 4 for making a test piece, which is a square with a side SL of 80 mm and a thickness D of 3 mm shown in FIG. 1, in the resin flow direction MD and the resin flow direction. On the other hand, the TD is set in the perpendicular direction, and the shape of the test piece described in JIS K 7161 (2014) is 1/2 of the shape of the test piece 1B so that the creep deformation evaluation test can be performed in each direction from the positions shown in FIGS. A cut test piece was used for (half dumbbell).
　この試験片に対して、掴み具間距離５５ｍｍ、荷重１２．５ＭＰａにて引張クリープ処理を行い、試験開始して１分後から４０時間後の伸び（塑性変形）を測定した。クリープ比率は以下の式（３）で表される。 This test piece was subjected to tensile creep treatment at a distance between grippers of 55 mm and a load of 12.5 MPa, and the elongation (plastic deformation) was measured from 1 minute to 40 hours after the start of the test. The creep ratio is expressed by the following equation (3).
　クリープ比率（％）＝ＭＤ方向の塑性変形（ｍｍ）／ＴＤ方向の塑性変形（ｍｍ）×１００　　（３）。
（実施例１～７）
　シリンダー温度を３２０℃、スクリュー回転数を４００ｒｐｍに設定した、２６ｍｍ直径の中間添加口を有する２軸押出機（東芝機械（株）製ＴＥＭ－２６）を用いて、参考例で得たＰＰＳ樹脂（Ａ）１００重量部に対して非繊維系無機フィラー（Ｃ）および／またはその他樹脂（Ｄ）を、表１に示す重量比で原料供給口から添加して溶融状態とし、（Ｂ）異形断面形状ガラス繊維および／または（Ｂ’）繊維状充填材を表１に示す重量比で中間添加口から供給し、吐出量３０ｋｇ／時間で溶融混練してペレットを得た。このペレットを用いて前記の各特性を評価した。その結果を表１に併せて示す。 Creep ratio (%) = plastic deformation in the MD direction (mm) / plastic deformation in the TD direction (mm) × 100 (3).
(Examples 1 to 7)
The PPS resin obtained in the reference example using a twin-screw extruder (TEM-26 manufactured by Toshiba Machine Co., Ltd.) having an intermediate addition port with a diameter of 26 mm, in which the cylinder temperature was set to 320 ° C. and the screw rotation speed was set to 400 rpm. A) Non-fiber-based inorganic filler (C) and / or other resin (D) was added to 100 parts by weight from the raw material supply port at the weight ratio shown in Table 1 to bring it into a molten state, and (B) a modified cross-sectional shape. Glass fibers and / or (B') fibrous filler were supplied from the intermediate addition port at the weight ratio shown in Table 1 and melt-kneaded at a discharge rate of 30 kg / hour to obtain pellets. Each of the above characteristics was evaluated using this pellet. The results are also shown in Table 1.
　実施例１～７の結果より、本発明のＰＰＳ樹脂組成物は、低線膨張かつ低異方性、低膨潤性であることがわかった。 From the results of Examples 1 to 7, it was found that the PPS resin composition of the present invention has low linear expansion, low anisotropy, and low swelling property.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　（比較例１～７）
　実施例１～７で用いたのと同じ２軸押出機により、参考例で得たＰＰＳ樹脂（Ａ）１００重量部に対して非繊維系無機フィラー（Ｃ）および／またはその他樹脂（Ｄ）を、表２に示す重量比で原料供給口から添加して溶融状態とし、（Ｂ）異形断面形状ガラス繊維および／または（Ｂ’）繊維状充填材を表２に示す重量比で中間添加口から供給し、吐出量３０ｋｇ／時間で溶融混練してペレットを得た。このペレットを用いて前記の各特性を評価した。その結果を表２に併せて示す。 (Comparative Examples 1 to 7)
Using the same twin-screw extruder used in Examples 1 to 7, the non-fiber-based inorganic filler (C) and / or other resin (D) was added to 100 parts by weight of the PPS resin (A) obtained in the reference example. , Add from the raw material supply port at the weight ratio shown in Table 2 to make it in a molten state, and add (B) irregular cross-sectional shape glass fiber and / or (B') fibrous filler from the intermediate addition port at the weight ratio shown in Table 2. It was supplied and melt-kneaded at a discharge rate of 30 kg / hour to obtain pellets. Each of the above characteristics was evaluated using this pellet. The results are also shown in Table 2.
　比較例１は、異形断面ガラス繊維を用いていないことから線膨張係数が大きく、異方性が生じていることがわかった。さらに、ガラス繊維と非繊維状充填材との比率が１未満であるため膨潤性も劣ることがわかった。 It was found that Comparative Example 1 had a large coefficient of linear expansion and anisotropy because it did not use glass fibers with a modified cross section. Furthermore, it was found that the swellability was also inferior because the ratio of the glass fiber to the non-fibrous filler was less than 1.
　比較例２および３は、異形断面ガラス繊維を用いていないことから線膨張係数が大きく、異方性が生じていることがわかった。一方で、ガラス繊維と非繊維状充填材との比率１未満であるため、膨潤性が劣ることがわかった。 It was found that Comparative Examples 2 and 3 had a large coefficient of linear expansion and anisotropy because they did not use glass fibers having a modified cross section. On the other hand, it was found that the swellability was inferior because the ratio of the glass fiber to the non-fibrous filler was less than 1.
　比較例４および５は、異形断面ガラス繊維を用いているため線膨張係数は抑えられているが、非繊維状充填材が多いため、つまりＸ／Ｙが７以上であるため線膨張係数の異方性が十分には抑制されていなかった。 In Comparative Examples 4 and 5, the linear expansion coefficient is suppressed because the glass fiber having an anisotropic cross section is used, but the linear expansion coefficient is different because there are many non-fibrous fillers, that is, because X / Y is 7 or more. Anisotropy was not sufficiently suppressed.
　比較例６は、異形断面ガラス繊維を用いているため線膨張係数は抑えられているが、異形断面ガラス繊維と非繊維状充填材とが同量入っているため（Ｘ／Ｙが１であるため）異方性が生じていた。 In Comparative Example 6, since the glass fiber having a deformed cross section is used, the coefficient of linear expansion is suppressed, but since the glass fiber having a deformed cross section and the non-fibrous filler are contained in the same amount (X / Y is 1). Because) anisotropy was generated.
　比較例７は、モース硬度の低いタルクを使用したため線膨張異方性差が大きくなることが分かった。加えて、実施例３と比較して、大幅な強度の低下も生じていることが分かった。 In Comparative Example 7, it was found that the difference in linear expansion anisotropy was large because talc having a low Mohs hardness was used. In addition, it was found that a significant decrease in strength also occurred as compared with Example 3.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　本発明のＰＰＳ樹脂組成物は、射出成形、押出成形、ブロー成形、トランスファー成形など各種成形に供することが可能であるが、特に射出成形用途に適している。 The PPS resin composition of the present invention can be used for various moldings such as injection molding, extrusion molding, blow molding, and transfer molding, but is particularly suitable for injection molding applications.
　以上のように、本発明に用いられるＰＰＳ樹脂組成物は、本来有する優れた機械物性、耐薬品性などの諸物性を大きく損なうことなく、線膨張係数およびクリープ変形において低異方性に優れたＰＰＳ樹脂組成物を得ることができる。そのため、寸法精度が求められる、かつ接触圧力で物品を保持するような成形品に有用である。特に、光学特性が要求される光学機器や精密機器関連は、寸法安定性およびレンズ圧入時のクリープ変形の異方性が少ないことが求められることから、これらの用途においては本発明の樹脂組成物が非常に有用である。具体的には、顕微鏡、双眼鏡、カメラ、時計などのレンズが圧入される用途が挙げられる。 As described above, the PPS resin composition used in the present invention is excellent in low anisotropy in linear expansion coefficient and creep deformation without significantly impairing various physical properties such as inherent excellent mechanical properties and chemical resistance. A PPS resin composition can be obtained. Therefore, it is useful for molded products that require dimensional accuracy and hold articles under contact pressure. In particular, optical instruments and precision instruments that require optical characteristics are required to have dimensional stability and less anisotropy of creep deformation during lens press-fitting. Therefore, the resin composition of the present invention is used in these applications. Is very useful. Specific examples include applications in which lenses such as microscopes, binoculars, cameras, and watches are press-fitted.
　その他、本発明のＰＰＳ樹脂組成物の適用可能な用途としては、例えばセンサー、ＬＥＤランプ、民生用コネクター、ソケット、抵抗器、リレーケース、スイッチ、コイルボビン、コンデンサー、バリコンケース、発振子、各種端子板、変成器、プラグ、プリント基板、チューナー、スピーカー、マイクロフォン、ヘッドフォン、小型モーター、磁気ヘッドベース、半導体、液晶、ＦＤＤキャリッジ、ＦＤＤシャーシ、モーターブラッシュホルダー、パラボラアンテナ、コンピューター関連部品などに代表される電気・電子部品；ＶＴＲ部品、テレビ部品、アイロン、ヘアードライヤー、炊飯器部品、電子レンジ部品、音響部品、オーディオ・レーザーディスク(登録商標)・コンパクトディスクなどの音声機器部品、照明部品、冷蔵庫部品、エアコン部品、タイプライター部品、ワードプロセッサー部品などに代表される家庭、事務電気製品部品への適用も可能である。その他、オフィスコンピューター関連部品、電話器関連部品、ファクシミリ関連部品、複写機関連部品、洗浄用治具、モーター部品、ライター、タイプライターなどに代表される機械関連部品：水道蛇口コマ、混合水栓、ポンプ部品、パイプジョイント、水量調節弁、逃がし弁、湯温センサー、水量センサー、水道メーターハウジングなどの水廻り部品；バルブオルタネーターターミナル、オルタネーターコネクター、ＩＣレギュレーター、ライトディマー用ポテンシオメーターベース、排気ガスバルブなどの各種バルブ、燃料関係・排気系・吸気系各種パイプ、エアーインテークノズルスノーケル、インテークマニホールド、燃料ポンプ、エンジン冷却水ジョイント、キャブレターメインボディー、キャブレタースペーサー、排気ガスセンサー、冷却水センサー、油温センサー、スロットルポジションセンサー、クランクシャフトポジションセンサー、エアーフローメーター、ブレーキパッド摩耗センサー、エアコン用サーモスタットベース、暖房温風フローコントロールバルブ、ラジエーターモーター用ブラッシュホルダー、ウォーターポンプインペラー、ウォーターポンプハウジング、エンジン冷却モジュール、タービンベイン、ワイパーモーター関係部品、デュストリビューター、スタータースイッチ、スターターリレー、トランスミッション用ワイヤーハーネス、ウィンドウォッシャーノズル、エアコンパネルスイッチ基板、燃料関係電磁気弁用コイル、ヒューズ用コネクター、ホーンターミナル、電装部品絶縁板、ステップモーターローター、ランプソケット、ランプリフレクター、ランプハウジング、ブレーキピストン、ソレノイドボビン、エンジンオイルフィルター、点火装置ケース、車速センサー、ケーブルライナーなどの自動車・車両関連部品など各種用途が例示できる。 Other applicable uses of the PPS resin composition of the present invention include, for example, sensors, LED lamps, consumer connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, oscillators, and various terminal boards. , Transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, semiconductors, liquid crystal, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, etc.・ Electronic parts: VTR parts, TV parts, irons, hair dryers, rice cooker parts, microphone parts, acoustic parts, audio / laser discs (registered trademark) ・ Audio equipment parts such as compact discs, lighting parts, refrigerator parts, air conditioners It can also be applied to household and office electrical product parts such as parts, typewriter parts, and word processor parts. Other machine-related parts such as office computer-related parts, telephone equipment-related parts, facsimile-related parts, copying machine-related parts, cleaning jigs, motor parts, writers, typewriters, etc .: Water faucet pieces, mixing faucets, Pump parts, pipe joints, water volume control valves, relief valves, hot water temperature sensors, water volume sensors, water meter housings and other water-related parts; valve alternator terminals, alternator connectors, IC regulators, light dimmer potentiometer bases, exhaust gas valves, etc. Various valves, fuel-related / exhaust system / intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, Throttle position sensor, crank shaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, water pump housing, engine cooling module, turbine vane , Wiper motor related parts, Dustributor, Starter switch, Starter relay, Transmission wire harness, Window washer nozzle, Air conditioner panel switch board, Fuel related electromagnetic valve coil, Fuse connector, Horn terminal, Electrical component insulation plate, Step Various applications such as motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, vehicle speed sensors, cable liners, and other automobile / vehicle-related parts can be exemplified.
１　スプルー
２　ランナー
３　ゲート
４　試験片作成のための切削加工用平板
５、６　切削加工用平板から作成された試験片 1 Sprue 2 Runner 3 Gate 4 Cutting plate for making test pieces 5, 6 Specimen made from cutting plate

Claims (7)

  1. （Ａ）ポリフェニレンサルファイド樹脂１００重量部に対して、（Ｂ）異形断面ガラス繊維を１００～２５０重量部、および（Ｃ）以下の（Ｃ－ａ）および（Ｃ－ｂ）を満たす非繊維系無機フィラーを２５～１５０重量部配合してなるポリフェニレンサルファイド樹脂組成物であって、前記（Ｂ）異形断面ガラス繊維の配合重量Ｘと前記（Ｃ）非繊維系無機フィラーの配合重量Ｙとの比率Ｘ／Ｙが１より大きく７未満である、ポリフェニレンサルファイド樹脂組成物。
    （Ｃ－ａ）モース硬度が２を超え４未満
    （Ｃ－ｂ）融点もしくは軟化点が３８０℃以上     (A) 100 to 250 parts by weight of (B) irregularly shaped cross-sectional glass fiber with respect to 100 parts by weight of polyphenylene sulfide resin, and (C) non-fiber-based inorganic material satisfying (Ca) and (Cb) below. A polyphenylene sulfide resin composition containing 25 to 150 parts by weight of a filler, wherein the ratio X of the compounding weight X of the (B) modified cross-sectional glass fiber and the compounding weight Y of the (C) non-fiber-based inorganic filler. A polyphenylene sulfide resin composition in which / Y is greater than 1 and less than 7.
    (CA) Mohs hardness is more than 2 and less than 4 (Cb) Melting point or softening point is 380 ° C or higher
  2. 前記（Ｂ）異形断面ガラス繊維の長径（断面の最長の直線距離）と短径（長径と直角方向の最長の直線距離）の比が１．３～１０であることを特徴とする請求項１に記載のポリフェニレンサルファイド樹脂組成物。 (B) Claim 1 characterized in that the ratio of the major axis (the longest linear distance in the cross section) to the minor axis (the longest linear distance in the direction perpendicular to the major axis) of the irregularly shaped cross-sectional glass fiber is 1.3 to 10. The polyphenylene sulfide resin composition according to.
  3. 前記（Ａ）ポリフェニレンサルファイド樹脂１００重量部に対する（Ｂ）異形断面ガラス繊維の配合重量Ｘと前記（Ｃ）非繊維系無機フィラーの配合重量Ｙの比率Ｘ／Ｙが１より大きく５未満である請求項１または２に記載のポリフニレンサルファイド樹脂組成物。 Claim that the ratio X / Y of the compounding weight X of the (B) modified cross-sectional glass fiber to the compounding weight Y of the (C) non-fiber inorganic filler with respect to 100 parts by weight of the (A) polyphenylene sulfide resin is greater than 1 and less than 5. Item 2. The polyphenylene sulfide resin composition according to Item 1 or 2.
  4. 前記記載の（Ｃ）非繊維系無機フィラーが炭酸カルシウムであることを特徴とする請求項１から３のいずれかに記載のポリフェニレンサルファイド樹脂組成物。 The polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein the non-fiber-based inorganic filler according to (C) is calcium carbonate.
  5. 請求項１～４のいずれかに記載のポリフェニレンサルファイド樹脂組成物からなる成形品。 A molded product comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 4.
  6. 成形品が筐体部品である請求項５の成形品。 The molded product according to claim 5, wherein the molded product is a housing component.
  7. （Ａ）ポリフェニレンサルファイド樹脂１００重量部に対して、（Ｂ）異形断面ガラス繊維を１００～２５０重量部、および（Ｃ）非繊維系無機フィラー（但し、六方晶窒化ホウ素、水酸化マグネシウム、タルク、酸化マグネシウム、および窒化アルミニウムを除く）を２５～１５０重量部配合してなるポリフェニレンサルファイド樹脂組成物であって、 前記（Ｂ）異形断面ガラス繊維の配合重量Ｘと前記（Ｃ）非繊維系無機フィラーの配合重量Ｙとの比率Ｘ／Ｙが１より大きく７未満である、ポリフェニレンサルファイド樹脂組成物。 For 100 parts by weight of (A) polyphenylene sulfide resin, (B) 100 to 250 parts by weight of modified cross-sectional glass fiber, and (C) non-fiber inorganic filler (however, hexagonal boron nitride, magnesium hydroxide, talc, etc. A polyphenylene sulfide resin composition comprising 25 to 150 parts by weight of magnesium oxide (excluding magnesium oxide and aluminum nitride), wherein the compounding weight X of the (B) modified cross-sectional glass fiber and the (C) non-fiber-based inorganic filler are described. A polyphenylene sulfide resin composition having a ratio X / Y to a compounding weight Y of more than 1 and less than 7.
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